Book of Abstracts

th

The 14 International Symposium on Inorganic Ring Systems July 26th – July 31st 2015 University of Regensburg 93040 Regensburg Germany

www.iris14.de

Program and Abstracts IRIS occurs every three years and is the premier international showcase for Main Group Chemistry, including Organometallic Chemistry and Inorganic Materials Chemistry. The IRIS meetings bring together leading professors, postdoctoral fellows and research students from around the world.

The History of IRIS Year

Town

Country

Host/Chair

IRIS-1

1975

Besancon

France

H. Garcia-Fernandez

IRIS-1b

1977

Madrid

Spain

H. Garcia-Fernandez

IRIS-2

1978

Göttingen

Germany

O. Glemser

IRIS-3

1981

Graz

Austria

E. Hengge

IRIS-4

1985

Paris

France

H. Garcia-Fernandez

IRIS-5

1988

Amherst

Massachusetts, USA

R. R. Holmes

IRIS-6

1991

Berlin

Germany

R. Steudel

IRIS-7

1994

Banff

Alberta, Canada

T. Chivers

IRIS-8

1997

Loughborough

UK

J. D. Woollins

IRIS-9

2000

Saarbrücken

Germany

M. Veith

IRIS-10

2003

Burlington

Vermont, USA

C. Allen

IRIS-11

2006

Oulu

Finland

R. S. Laitinen

IRIS-12

2009

Goa

India

P. Mathur

IRIS-13

2012

Victoria, B.C.

Canada

N. Burford

Message from Nikolaus Korber Senior Vice President, University of Regensburg

Welcome to the 14th International Symposium on Inorganic Ring Systems and welcome to Regensburg. The University of Regensburg is honored to be hosting the premier international forum for Main Group Chemistry. The IRIS-14 conference provides an excellent opportunity to raise national and international collaboration in this important research field. Chemistry plays a central role in many of the University of Regensburg’s research strengths. Our highly successful and internationally recognized Faculty of Chemistry and Pharmacy is excited to organize IRIS-14 as showcase for promoting world-class research and outstanding chemical education. I hope you will enjoy your time with us in Regensburg. Our city also has a special historical link to chemistry: Albert the Great, author of the first medieval chemical textbook “De Mineralibus” and discoverer of the element arsenic, was bishop of Regensburg from 1260 to 1262.

Prof. Dr. Nikolaus Korber Senior Vice President University of Regensburg

Welcome Message from Manfred Scheer Symposium Chair

Welcome to the 14th International Conference on Inorganic Ring Systems and welcome to the historic city of Regensburg. Located on the northernmost point of the Danube River, the old town of Regensburg together with the suburb Stadtamhof is an exceptional example of a Central European medieval trading centre. The rich interchange of cultural and architectural influences can be seen across the city until this day. Regensburg’s 11th- to 13th-century architecture still defines the character of the town. The historic buildings include medieval patrician houses and towers, a large number of churches and monastic ensembles, including St. Peter’s Cathedral, as well as the 12th-century Stone Bridge. Since July 2006, Regensburg has been inscribed on the UNESCO list of World Heritage Sites. Nevertheless, with more than 155,000 inhabitants and almost 30,000 students, Regensburg is a young and modern city. The University of Regensburg, founded in 1962, is located south of the downtown area. On its campus IRIS-14 will take place. The program of the conference starts with an opening mixer on Sunday evening at the Old Town Hall, which was home to the so-called “Eternal Diet”, the parliament of the Holy Roman Empire, for two centuries from 1663 until 1806. The scientific oral presentations (25 plenary and keynote lectures and 63 oral presentations) are scheduled from Monday morning to Friday noon, with poster sessions (175 posters) on Monday and Tuesday evening. I am grateful for the excellent advice and support of my colleagues on the International Advisory Board, the National Advisory Committee and the Local Organizing Committee during the development of this exciting program. On Wednesday afternoon there will be an excursion in the form of a boat trip on the Danube to the Walhalla memorial (neo-classical German hall of fame), and on Thursday evening the symposium banquet will take place in the Minorites Church, which is part of the Historical Museum of the City of Regensburg. I hope all of the 342 participants from 22 countries will very much enjoy this great meeting of contemporary main group chemistry. We are grateful for the financial support of the sponsors who have contributed to this event.

Manfred Scheer Symposium Chair University of Regensburg

The organizers acknowledge the generous support of the following sponsors:

IRIS-14 International Advisory Board C. W. Allen (USA)

M. Scheer (Germany)

T. Chivers (Canada)

R. Streubel (Germany)

A. H. Cowley (USA)

N. Tokitoh (Japan)

R. R. Holmes (USA)

R. Uhlig (Austria)

R. Laitinen (Finland)

M. Veith (Germany)

N. Burford (Canada)

R. West (USA)

P. Mathur (India)

J. D. Woollins (UK)

H. W. Roesky (Germany)

IRIS-14 National Advisory Committee J. Beckmann (Bremen)

D. Scheschkewitz (Saarbrücken)

H. Braunschweig (Würzburg)

A. Schnepf (Tübingen)

R. Breher (Karlsruhe)

A. Schulz (Rostock)

S. Dehnen (Marburg)

U. Siemeling (Kassel)

D. Gudat (Stuttgart)

D. Stalke (Göttingen)

S. Harder (Erlangen)

R. Streubel (Bonn)

E. Hey-Hawkins (Leipzig)

W. Uhl (Münster)

K. Jurkschat (Dortmund)

M. Wagner (Frankfurt/M.)

M. Mehring (Chemnitz)

J. Weigand (Dresden)

R. Pietschnig (Kassel)

IRIS-14 Local Organizing Committee Manfred Scheer, Symposium Chair Gábor Balázs Karin Kilgert Eva-Maria Rummel

With additional contribution of Robert Kretschmer

Christian Marquardt

Martina Amann

Daniela Meyer

Katharina Baier

Moritz Modl

Michael Bodensteiner

Julian Müller

Jens Braese

Eugenia Peresypkina

Helena Brake

Felix Riedlberger

Luis Duetsch

Reinhard Rund

Mehdi Elsayed Moussa

Thomas Schottenhammer

Martin Fleischmann

Monika Schmidt

Oliver Hegen

Andrea Schreiner

Claudia Heindl

Michael Seidl

Tobias Kahoun

Andreas Seitz

David Konieczny

Fabian Spitzer

Barbara Krämer

Andreas Stauber

Giuliano Lassandro

Valentin Vass

Petra Lugauer

Alexander Virovets

Eric Mädl

Rudolf Weinzierl

IRIS-14 Schedule of Events at a Glance Sunday, July 26th 8:30 8:50 9:00 9:10 9:20 9:30 9:40 9:50 10:00 10:10 10:20 10:30 10:40 10:50 11:00 11:10 11:20 11:30 11:40 11:50 12:00 12:10 12:20 12:30

Monday, July 27th Registration Welcome

Tuesday, July 28th

Wednesday, July 29th

Registration

Registration

PL1 R. Mulvey

PL3 C. Cummins

PL5 H. Grützmacher

PL7 T. Fäßler

KL1 H. Braunschweig

KL4 E. Hevia

KL7 C. Jones

KL10 I. Manners

KL2 A. Schulz

KL5 G. Bertrand

KL8 C-W. Chiu

KL11 E. Rivard

KL14 J. Goicoechea

Coffee Break

Coffee Break

Coffee Break

Coffee Break

KL15 S. Harder

KL6 D. Scheschkewitz

KL9 G. Robinson

KL12 S. Yamaguchi

Coffee Break

PL4 D. Stephan

PL6 F. Gabbaï

KL13 L. Berben

KL16 I. Krossing

PL2 N. Burford KL3 D. Bourissou

12:10 – 1:40 Lunch

Thursday, July 30th

PL8 S. Aldridge

12:00 – 1:40 Lunch

12:10 – 1:40 Lunch

----13:40 13:50 14:00 14:10 14:20 14:30 14:40 14:50 15:00 15:10 15:20 15:30 15:40 15:50 16:00 16:10 16:20 16:30 16:40 16:50 17:00 ----19:00 21:00

16:00 Registration

A1 C. Russell A2 D. P. Gates A3 F. Dielmann A4 J. Weigand A5 P. Pringle

B1 M. Beckett B2 T. Agou B3 A. Timoshkin B4 H. Bettinger B5 A. Ruzicka

A10 R. Streubel A11 L. Nyulaszi A12 E. Hey-Hawkins A13 R. Pietschnig A14 F. Uhlig

B10 S. Konchenko B11 R. Layfield B12 L. Dostal B13 R. Waterman B14 D. Gudat

C1 G. Balázs C2 R. Murugavel C3 J. Corrigan C4 C. Strohmann C5 B. Ramamoorthy

Coffee Break

Coffee Break

Coffee Break

Coffee Break

A6 W. Uhl A7 C. Slootweg A8 R. Kretschmer A9 R. Melen

B6 T. Chivers B7 Y. Yamamoto B8 A. Zibarev B9 I. Vargas-Baca

A15 R. Fischer A16 R. Wolf A17 V. Lee A18 U. Siemling

B15 J. Beckmann B16 M. Cowley B17 W. Kaim B18 I. Bezkishko

Poster Session A Opening

Poster Session B

A19 T. Müller A20 T. Iwamoto A21 T. Sasamori A22 L. Wesemann A23 M. Saito

B19 T. Baumgärtner B20 M. Veith B21 D. Stalke B22 R. Boeré B23 C. Macdonald

Coffee Break

Coffee Break

Coffee Break

C6 C. Tessier C7 Z. Benkö C8 M. Mosquera C9 G. Mloston

A24 A. Schnepf A25 S. Dehnen A26 C.-W. So A27 K. Jurkschat

B24 C. Lescop B25 C. Romero-Nieto B26 H. Stueger B27 M. Balakrishna

14:00-19:00 Excursion

July Friday, 31st

19:00-23:00 Banquet

KL17 N. Tokitoh 12:30 – 13:00 Closing remarks

Registration, Lunches and Social Events Registration Sunday, July 26th

4:00-7:00 p.m.

Monday, July 27th

8:30-9:00 a.m.

Tuesday, July 28th

8:30-9:00 a.m.

Wednesday, July 29th

8:30-9:00 a.m.

Thursday, July 30th

8:30-9:00 a.m.

at the Old Town Hall, Rathausplatz 1, 93053 Regensburg at the University of Regensburg, in the lobby of the central lecture hall H1

at the University of Regensburg, in the lobby of lecture hall H24

Opening Mixer Sunday, July 26th,

7:00-9:00 p.m.

at the Old Town Hall, Rathausplatz 1, 93053 Regensburg

Lunch Monday, July 27th

12:10-1:40 p.m.

Tuesday, July 28th

12:10-1:40 p.m.

Wednesday, July 29th

12:00 p.m.

at the University of Regensburg, in the lobby of lecture hall H24 (Lunchbox)

Thursday, July 30th

12:10-1:40 p.m.

at the University of Regensburg, in the lobby of the central lecture hall H1

at the University of Regensburg, in the lobby of the central lecture hall H1

Boat Trip on the Danube to the Walhalla with the “Kristallkönigin” (crystal queen) boat: Wednesday, July 29th, 2:00 p.m., boarding and landing at the “Eiserne Brücke”

Conference Dinner Thursday, July 30th, 7:00-9:00 p.m. at Minoritenkirche (Minorites Church, part of the Historic Museum of the City of Regensburg), Dachauplatz 2-4, 93047 Regensburg

Scientific Program

Timetable Monday, July 27th H1

Chair: M. Scheer

PL01 9:00

Robert E. Mulvey

KL01 9:40

Holger Braunschweig

KL02 10:10 Axel Schulz

Template Ring Approaches to Metallation Chemistry Cyclic and Acyclic Boron-based Chromophores: Highly Unusual Donor-Acceptor Systems Activation of Small Molecules by Biradicaloids

10:40 Coffee Break H1

Chair: W. Uhl

PL02 11:00 Neil Burford KL03 11:40 Didier Bourissou

Evolving the Coordination Chemistry of p-Block Element Lewis Acceptors Boron-Cations and Radicals Stabilized by Strong P→B Interactions

Lunch H2

Chair: E. HeyHawkins

A01

13:40 Chris Russell

A02

14:00 Derek P. Gates

A03

14:20 Fabian Dielmann

A04

14:40 Jan J. Weigand

A05

15:00 Paul Pringle H3

Main Group Elements as Transition Metals: Reactions of Phosphorus-Carbon Multiple Bonds with Small Molecules The Addition-Isomerization Polymerization of Phosphaalkenes Highly electron-rich phosphines for the activation of small molecules Synthesis and Reactivity of a Zwitterionic Diphosphanide 'Inorganic' Arylphosphines

Chair: D. Stalke

B01

13:40 Michael Beckett

B02

14:00 Tomohiro Agou

B03

14:20 Alexey Timoshkin

B04

14:40 Holger Bettinger

B05

15:00 Ales Ruzicka

New isolated polyborate anions templated by cationic transition-metal complexes Reactivities of a Barrelene-type Dialumane as an Equivalent of an Al=Al Doubly-bonded Species Donor-acceptor complexes of inorganic analogs of benzene Multiply Boron-Nitrogen Doped Hexi-perihexabenzocoronene Main group metal complexes containing hybrid amino/guanidinate (1- or 2-) ligands

15:20 Coffee Break

Scientific Program

H2

Chair: S. Dehnen

A06

15:40 Werner Uhl

A07

16:00 Chris Slootweg

A08

16:20 Robert Kretschmer

A09

16:40 Rebecca Melen

H3

An Al/P Based Frustrated Lewis Pair as an Efficient Ambiphilic Ligand for the Coordination and Activation of Polar Compounds Cooperative Lewis Acid/Base Catalysis Subsequent Reduction of a Cyclic Alkyl (amino) carbene–SbCl3 Adduct – Access to Different Oxidation States of Antimony Activation of π-Bonds Towards Cyclization Reactions using Lewis Acidic Boranes

Chair: C. Allen

B06

15:40 Tristram Chivers

B07

16:00 Yohsuke Yamamoto

B08

16:20 Andrey Zibarev

B09

16:40 Ignacio Vargas-Baca

17:00 Poster Presentations

Chalcogen Macrocycles Incorporating P2N2 Rings and Coinage Metals Synthesis and Properties of Hypervalent Sulfur Radicals Synthesis and Characterization of Sulfur-Nitrogen πHeterocyclic Radical-Anion Salts with Sandwich Organometallic Cations The Supramolecular Chemistry of Iso-Tellurazole NOxides Uneven numbered Posters

Scientific Program

Tuesday, July 28th H1

Chair: F. Gabbai

PL03 9:00

Christopher C. Cummins

KL04 9:40

Eva Hevia

KL05 10:10 Guy Bertrand

Phosphorus-Containing Ring Systems from Low to High Oxidation States New main group-metal-mediated strategies for ring functionalisation Nucleophilic boron derivatives, stable phosphinidenes and other main group species

10:40 Coffee Break H1

Chair: R. Mulvey

KL06 11:00 David Scheschkewitz PL04 11:30 Doug Stephan

Base-Induced Isomerization of Unsaturated Group 14 Ring Systems FLP-rings: Applications in Synthesis and Catalysis

Lunch H2

Chair: D. Scheschkewitz

A10

13:40 Rainer Streubel

A11

14:00 Laszlo Nyulaszi

A12

14:20 Evamarie Hey-Hawkins

A13

14:40 Rudolf Pietschnig

A14

15:00 Frank Uhlig H3

Building Blocks for Smart Inorganic Polymers (SIPs CM1302) Super-strained inorganic ligands: substrate-dependent reactivity Hetero deoxy-Breslow intermediates – and more Unusual Reactivity of Alkali Metal Oligophosphanediides Stable Silanetriols – Building Blocks for Rings and Cages Cyclic Derivatives of Group 14 in Material Science

Chair: C. Russell

B10

13:40 Sergey Konchenko

B11

14:00 Richard Layfield

B12

14:20 Libor Dostál

B13

14:40 Rory Waterman

B14

15:00 Dietrich Gudat

Mixed d-/f-Metal Polypnictide Complexes Phosphorus, Arsenic and Antimony Ligands in Lanthanide Molecular Nanomagnets Quest for Monomeric Stibinidenes and Bismuthinidenes as New Ligands for Transition Metals Iron-Catalyzed Routes to Phosphorous-Containing Rings One, two, three Halogens on the Ring - on the Formation Mechanism of N-Heterocyclic Haloboranes and Halophosphanes

Scientific Program

H4

Chair: K. Jurkschat Complexes Containing W≡E (E = P, As and Sb) Triple Bond as Precursors for Linearly Coordinated EQ (Q = O, S, Se and Te) Ligands Is Single-4-Ring the Most Basic but Elusive Secondary Ramaswamy Murugavel Building Unit that Transforms to Larger Structures in Zinc Phosphate Chemistry? NHC Ligands for Ternary Metal-Chalcogen Cluster John F. Corrigan Assembly Reactivity and Structure-Building Principles of LiCKOR Carsten Strohmann Base Mixtures in THF Boomi Shankar Functional metal-organic molecules and materials Ramamoorthy derived from rigid and flexible P-N scaffolds

C1

13:40 Gábor Balázs

C2

14:00

C3

14:20

C4

14:40

C5

15:00

15:20 Coffee Break H2

Chair: T. Chivers

A15 15:40 Roland C. Fischer A16 16:00 Robert Wolf A17 16:20 Vladimir Lee A18 16:40 Ulrich Siemeling H3

Chair: R. Layfield

B15 15:40 Jens Beckmann B16 16:00 Michael J. Cowley B17 16:20 Wolfgang Kaim B18 16:40 Ilya Bezkishko

H4

15:40 Claire Tessier

C7

16:00 Zoltán Benkö Marta Elena Gonzalez 16:20 Mosquera

C9

Peri-Interactions within (Ace)Naphthyl Compounds Reloaded Synthesis and reactivity of phosphinidene boranes Unconventional Ring Sizes with Noninnocent Ligand Components The sodium 3,4,5-triaryl-1,2diphosphacyclopentadienides derivatives: synthesis and coordination properties

Chair: R. Streubel

C6

C8

Captivating Organotin Anions – Cages, Rings and Chains Transformations of Small Inorganic Molecules by Lowvalent Transition Metalate Anions and Transition Metal Radicals Pyramidanes: the Covalent Form of an Ionic Compound Stable N-Heterocyclic Carbenes with a 1,1’Ferrocenediyl Backbone and Their Heavier Homologues

16:40 Grzegorz Mloston

17:00 Poster Presentations

Chlorine/oxygen transfer reactions of [PCl2N]3 using oxygenated Lewis bases as a possible route to [PON]3 Phosphorus heterocycles from Na(OCP) Terpene Main Group Chiral Derivatives: Catalytic Activity in Polymerization and C-H Activation Processes Ferrocenyl Substituted 1,3-Dithiolanes via [3+2]Cycloadditions of Thiocarbonyl S-Methanides with Ferrocenyl/Hetaryl Thioketones Even numbered Posters

Scientific Program

Wednesday, July 29th H24 Chair: N. Burford PL05

9:00 Hansjörg Grützmacher

KL07 9:40 Cameron Jones KL08 10:10 Ching-Wen Chiu

New Phosphorus Heterocycles from Simple Building Blocks Low oxidation state main group compounds: stabilisation strategies and transition metal-like reactivity Boron Cations and Poly-dentate Divalent Group 14 Ligands

10:40 Coffee Break H24 Chair: G. Bertrand KL09 11:00 Greg Robinson PL06 11:30 François Gabbaï

From Metalloaromaticity to N-Heterocyclic Carbenes: The Evolution of Inorganic Rings Lewis acidic and redox properties of organoantimony derivatives – Applications in anion sensing and halogen photoreductive elimination

Lunch 14:00 Boat trip

Scientific Program

Thursday, July 30th H24 Chair: I. Krossing PL07

9:00 Thomas Fässler

KL10 9:40 Ian Manners KL11 10:10 Eric Rivard

Group 14 element rich cages and rings as precursors and intermediates for the formation of intermetalloid clusters Catalysis in Service of Main Group Chemistry: MetalMediated and Metal-Free Routes to Molecules and Materials based on Elements from Group 13-15 Inorganic Heterocycles: From New Light-emitting Entities to Surprising Products from Ligand Activation

10:40 Coffee Break H24 Chair: M. Veith KL12 11:00 Shigehiro Yamaguchi

Main group strategy for photo and electronic functions

KL13 11:30 Louise Berben

Ligand-Based Redox Chemistry with Aluminum(III)

Lunch H43 Chair: D. Gudat A19

13:40 Thomas Müller

A20

14:00 Takeaki Iwamoto

A21

14:20 Takahiro Sasamori

A22

14:40 Lars Wesemann

A23

15:00 Masaichi Saito

Transformations of Small Inorganic Molecules by Lowvalent Transition Metalate Anions and Transition Metal Radicals Reactions of tricyclopentasilane and related cyclic silicon compounds with bulky alkyl substituents Synthesis of 1,2-Digermacyclobutene Derivatives and Their Reactions with Ethylene Synthesis, Molecular Structure and Reactivity of Cyclic Sn–P-Lewis Pairs Synthesis, Structures and Reactions of Antiaromatic Organolead Compounds Stabilized by Lewis Bases

H44 Chair: D. Woollins B19

13:40 Thomas Baumgartner

B20

14:00 Michael Veith

B21

14:20 Dietmar Stalke

B22

14:40 René Boeré

B23

15:00 Charles Macdonald

Laterally-Functionalized Phospholes – Versatile Building Blocks for π-Conjugated Materials From cyclic and polycyclic alkoxoaluminium hydrides to alumina composites with nano- and micro-meter rings and cages A World of Difference – Alkali Metal Organic Frameworks From Ammonia Coordination Polymers from Main Group Ring Compounds Ligand Chemistry of Stable Phosphorus(I) Compounds

15:20 Coffee Break

Scientific Program

H43 Chair: L. Wesemann A24

15:40 Andreas Schnepf

Chemistry Applying Metalloid Tin Clusters Ternary Intermetalloid Clusters: About Unexpected Structures and How to Get There Base-Stabilized Low Valent Group 14 Element Complexes for the Construction of Unsaturated Systems Anion and Cation Complexation by Di- and Multicentered Tin-Based Lewis Acids

A25

16:00 Stefanie Dehnen

A26

16:20 Cheuk-Wai So

A27

16:40 Klaus Jurkschat

B24

Chair: T. Baumgärtner 15:40 Christophe Lescop

B25

16:00 Carlos Romero-Nieto

B26

16:20 Harald Stueger

B27

16:40 Maravanji Balakrishna Cyclodiphosphazanes in Metal Organic Frameworks

H44

Thermochromic Emissive Metallacycles Paving the Way to Novel Phosphorus-based Architectures: a Non-catalyzed Protocol to Access Fused Heterocycles Photoinduced Rearrangement of Acylcyclopolysilanes

19:00 Conference Dinner

Scientific Program

Friday, 31 July H24 Chair: C. Jones PL08

9:30 Simon Aldridge

KL14 10:10 Jose Goicoechea KL15 10:40 Sjoerd Harder

Novel approaches to E-H bond activation and functionalization using Main Group systems Novel Phosphorus ring systems derived from the 2phosphaethynolate anion Early Main Group Metal Hydride Complexes

11:10 Coffee Break H24 Chair: T. Fäßler KL16 11:30 Ingo Krossing KL17 12:00 Norihiro Tokitoh

Bermuda-Clusters…? On the Interaction of Chelating Bipyridines with Subvalent Ga+ and In+ Salts of the [Al(ORF)4]– WCA New Aspects in the Chemistry of Al-containing Cyclic Compounds

12:30 Closing Remarks

Scientific Program

Contributed Poster Presentations Poster no P001 P002 P003 P004 P005 P006 P007 P008 P009 P010 P011 P012 P013 P014 P015 P016 P017 P018 P019 P020 P021 P022 P023 P024 P025 P026

Presenter Naoki Ando Evgeny Kolychev

Title of the Abstract Photocyclization of Dimesitylborylarenes Chelating bis(diazaboryl) ligands for preparation of cyclic bisboryl complexes Jesus Campos Synthetic Applications of Borylzinc Compounds: Boryl Transfer Manzano Chemistry and Catalytic Borylation. Harmen Zijlstra Well-Defined Boralumoxanes as Convenient MAO Modelling Compounds Charlotte Jones Syntheses, structural characterization and DFT investigations of pentaborate salts templated by substituted pyrrolidinium cations Jiří Böserle Study of reactivity of germylene stabilized by boraguanidinate ligand Koichi Nagata Reactions of a Barrelene-type Dialumane Bearing Bulky Aryl Substituents with Lewis Bases Tomas Chlupaty In-Situ Activation of C-C Multiple Bonds Mediated by Amidinato-Aluminium Framework María Teresa Muñoz- New aluminate compounds of low nuclearity: synthesis and Fernández catalytic activity studies. Mahendra Kumar Aminotroponate ligand stabilized pentacoordinate Aluminium Sharma (III) complexes Glen Briand “Strained” Metal Bonding Environments in Indium(III) Dithiolates and Their Use as Lewis Acid Catalysts Daniel Franz Aluminacycles Derived from the Imidazolin-2-iminato Ligand Manuel Kapitein NHC-stabilized Silylphosphinoalanes / -gallanes Tomáš Řičica Reactivity of N→Ga Coordinated Organogallium compounds Katharina Hanau Synthesis of Gallium Chalcogenide Clusters with Organic Functionality Jana Weßing Hume-Rothery Phase-inspired molecular chemistry – Synthesis of intermetalloid transition metal/group 13 clusters Andreas Kirchmeier The impact of silyl-groups in β-position on the electronic systems of phospholes Marius Arz n and π Complexes of NHC-stabilized Disilicon(0) Henning A H-substituted Silylium Ion Großekappenberg Fabian Uhlemann [Si3Cl5(NHC)3]+: An unprecedented Silyl Cation obtained from metastable SiCl2 Solution Dennis Lutters Activation of 7-Silanorbornadienes by NHCs – A Fast and Selective Way to NHC Stabilized Hydridosilylenes Yuk Chi Chan Synthesis and Reactivity of an NHC-stabilized Silicon(I) Dimer Isabell Omlor The Silyldisilene-Cyclotrisilane Equilibrium Hui Zhao Reactivity of cyclotrisilene with multiply-bonded molecules Bernhard Baars Metal-Silicon Triple Bonds: [2+2] Cycloadditions of Alkynes and Heteroalkynes Dominik Keiper Consecutive Synthesis of Novel Cagelike Bicyclic Trisiloxanes

Poster Contributions

Poster no P027

Presenter Priyabrata Ghana

P028

Carsten Eisenhut

P029 P030

Miroslav Novák Kerstin Hansen

P031

Nora Breit

P032

Sabrina Khoo

P033

Kirsten Reuter

P034 P035

Leon Van Der Boon Philipp Willmes

P036

Christa Grogger

P037

Christopher Golz

P038 P039 P040 P041

Tomohiro Sugahara Crispin Reinhold Dominik Schnalzer Michael Haas

P042

Lena Albers

P043

Kathrin Louven

P044

Kai Schwedtmann

P045

Jordan Waters

P046

David Nieder

P047 P048

Zsolt Kelemen Arnab Rit

P049 P050 P051

Jan Oetzel Jessica Edrich Cem Burak Yildiz

P052

Jan Turek

P053 P054

Niklas Rinn Olga Gapurenko

Title of the Abstract Metal─Silicon Multiple Bonds: Metallasilylidynes and Metallasilacumulenes The Versatile Reactivity of an NHC-stabilized Silicon(II) Monohydride Synthesis of Intramolecularly Coordinated Organosilanes A Highly Reactive “Half-Parent” Phosphasilene and Iminosilane LSi=EH (E = N, P) Reactivity of Phosphorus-functionalized Low-valent Silicon Compounds towards Transition Metal Complexes A Low Valent Silicon-Rhodium and -Cobalt Four-Membered Ring Synthesis and Properties of Silicon Based Crown Ether Analogues Configurationally Stable Pentaorganosilicates Functionalization and Transfer of Unsaturated Si6 Cluster Compounds Synthesis and Characterization of Cyclic Acylsilanes Precursors for Brook-Type Cyclic Silenes 2-(Dimethylaminomethyl)-ferrocenyl Substituted Silanols, Disilanolates and Siloxanes: Search for new Intermediates Synthesis and Structure of a Stable 1,2-Digermabenzene Sila- and Germacyclopentadienyl Radicals vs. Anions Photochemical Reactivity of Cyclic Acylgermanes Synthesis and Characterization of the first relatively stable Germenolates Cationic Rearrangements in Polysilanes and Polygermasilanes Subtle Capture of Intermediates Is Me3SiOK a Substitute for Me3COK in Schlosser’s Base Mixtures? Syntheses and Reactions of Cationic 4-Phosphonio Substituted NHCs Synthesis and Reactivity of Ditopic Carbanionic N-Heterocyclic Carbene Complexes Reactivity of heavier NHC-coordinated Vinylidene Analogues towards Anionic Nucleophiles Stability and Structure of Ferrocene based Carbene Analogues Acyclic Two-Coordinate Cationic Germylenes – Metal Element Bond Formation Ferrocene-based Tetrylenes Cyclic distannene in reaction with terminal alkynes Reductive Cleavage of the CO Triple Bond by an Anionic Lowvalent Maingroup Species A Computational Chemistry Quest for Viable and Stable Tin(0) Compounds, The Stannylones. Functional Binary and Ternary Organotin Selenide Clusters Group 14 element pyramidanes: theoretical studies

Poster Contributions

Poster no P055 P056 P057

Presenter Stefan Mitzinger Roman Jambor Denis Kargin

P058 P059

Lies Broeckaert Robert Wilson

P060

Bastian Weinert

P061 P062 P063

O. Kysliak Tatsumi Ochiai Jan Vrána

P064

Kilian Krebs

P065

Julia Schneider

P066

Petr Svec

P067

Paul Gray

P068

Christian Sindlinger

P069 P070 P071 P072

Justin Frank Binder Alexander Hinz Thomas Robinson Stefan Weller

P073 P074

Stefan Borucki Adinarayana Doddi

P075

Otfried Lemp

P076 P077 P078

Stephanie Kosnik Alicia López Andarias Payal Malik

P079

Michael Seidl

P080

Philip Junker

P081 P082

Siu Kwan Lo Melina Klein

Title of the Abstract Quantitative Understanding of Multimetallic Cluster Growth Chemistry of Intramolecularly Coordinated Stannylenes Stereoselective approaches towards bisphosphano substituted tetrylenes via [3]-ferrocenophanes Formation and Functionalization of Intermetalloid Clusters Reactivity of M/14/15 Intermetalloid Clusters Toward Organic and Main Group Organometallic Compounds An Efficient Approach to Ternary Intermetalloid Clusters and Novel Zintl Ions Subsequent chemistry of Ge94- Zintl anion Synthesis and Reactivity of Novel Amino(imino)metallylenes Bis(amido)phosphanes and their use as ligands for 14th group metals η3-Allyl Coordination at Tin(II) – Reactivity towards Triplebonds Reversibility in reactions of cyclic distannenes with terminal alkynes under ambient conditions C,N-Chelated Organotin(IV) Azides as Precursors for Substituted Tetrazoles Preparation and Reactivity of Cationic Germanium(II) and Tin(II) Donor-Acceptor Complexes Versatile precursors: Organotin(IV) hydrides as building blocks for low-valent tin chemistry Carbene-Stabilized P(I) Cations The Reactivity of Heavy Group 15 Allyl Analogs PCO− as a Precursor to Novel P-Containing Heterocycles Synthesis and chemical studies of Diaza-phosphaferrocenophanes Ferrocenylene bridged Oligophosphanes N-Heterocyclic Carbene Phosphinidene and Phosphinidyne Metal Complexes and their Applications New Synthetic Approach to the Synthesis of NHCPhosphinidene Compounds Zwitterionic Triphospheniums as Multidentate Donors Synthesis and Photophysical Properties of Novel PhosphorusContaining Conjugated Systems Cycloaddition of P–C Single Bonds? The Case of Oxaphosphirane Complexes and ortho-Benzochinones Reactions of the Pentelidene Complexes [Cp*E{W(CO)5}2] (E = P, As) with Heterocumulenes 1,3,2-Dioxaphosphol-4-enes: synthesis of a novel inorganic ring system Synthesis of asymmetric phosphorus diiminopydrine complexes Synthesis, thermolysis and photochemistry of oxaphosphirane complexes

Poster Contributions

Poster no P083 P084 P085 P086

Presenter Cristina Murcia García Christian Roedl Eva-Maria Rummel Elif Şenkuytu

P087

Serap Beşli

P088

Yasemin Tümer

P089

Ceylan Mutlu

P090

Aylin Uslu

P091

Markus Blum

P092

Imtiaz Begum

P093 P094

Jan Faßbender Rosalyn Falconer

P095

Jonas Bresien

P096

Lukas Guggolz

P097

Jaap E. Borger

P098 P099 P100

Fabian Spitzer Andreas Seitz Khatera Hazin

P101

René Labbow

P102 P103 P104

Sivathmeehan Yogendra Roman Olejník Andrew Jupp

P105

Martin Fleischmann

P106

Jonathan Dube

P107

Ralf Kather

Title of the Abstract Fluorinated oxaphosphirane complexes: synthesis, redox potentials and novel reactions Bimetallic 1,3 Diphosphacyclobutadiene Sandwich Compounds Oxidation and Isomerization of Diphosphete Complexes Structural Properties of Paraben Substituted FluorenylideneDouble Bridged Cyclophosphazenes The synthesis and characterization of spiro bridged cyclophosphazene compounds containing two chiral centers Syntheses, structural characterizations of new phosphazenes bearing vanillinato and pendant monoferrocenyl groups The substitution reactions of a mono ansa fluorodioxycyclotriphosphazene derivative with diols Cis- and trans-Azole Substituted Cyclotriphosphazene Derivatives A new insight into the homolytical bond dissociation of Tetraaminodiphosphines Synthesis of P-functional thiazole-2-thiones – precursors for NHCs? Exploring the accessibility of thiaphosphirane complexes anew 1,3,5-Triphosphabenzenes: Molecules with a Thirst for Hydrogen [ClP(µ-PMes*)]2 – A Versatile Reagent in Phosphorus Chemistry Binary, Protonated Seven-Atom Zintl Anions [H2GeP6]2– and [H2SiP6]2– Functionalization of P4 using Lewis acid-stabilized bicyclo[1.1.0]tetraphosphabutane anions Fixation and liberation of intact E4 tetrahedra (E = P, As) Functionalization of [Cpʹʹ2Zr(η1:1-P4)] Synthesis and Application of Weighable Brønsted Acids Containing Hexacoordinated Phosphorus(V) Anions N-Trimethylsilylsulfinylamine - Reactivity and Isomerisation Induced by Lewis Acids Synthesis and Reactivity of a Triflyloxyphosphonium Dication Synthesis and Structure of Terdentate Ketoiminate Complexes A Novel Synthesis of the 2-Phosphaethynolate Anion and Subsequent Reactivity Pentaphospha- and Pentaarsaferrocene - A Comparative Study of Their Coordination Ability Towards Weakly Coordinating Lewis Acids Chemistry of Cationic Arsines: A New Class of Electrophilic Ligands Reaction of the Lewis acid B(C6F5)3 with [Ph3SbO]2, Ph2P(O)OH and other Lewis bases containing oxygen acceptor atoms

Poster Contributions

Poster no P108 P109 P110 P111

Presenter Lukas Belter Monika Schmidt Iva Vránová Johanna Heine

P112 P113

Benjamin Ringler J. Derek Woollins

P114

P117

Lucia-Myongwon Lee Bronte Charette Nikolay Pushkarevsky Jamie Ritch

P118

Nikolay Semenov

P119

Jari Konu

P120

Róża Hamera

P121

Mansura Akter

P122 P123 P124

Carsten Donsbach Silke Santner Emanuel Hupf

P125

Martin Hejda

P126

Fabian Müller

P127

Titel Jurca

P128 P129 P130

Klara Edel Peter Grüninger Christian Marquardt

P131

Tom Stennett

P132

Niels Lichtenberger

P115 P116

Title of the Abstract Polycyclic Amides with As and Sb The reactivity of As4 towards transition metal complexes Stibinidine and Bismuthinidine as ligands for TM Using Supramolecular Interactions to shape new Halogenido Bismuthate Materials Syntheses of Binary Interpnictogenes and their Reactivity Investigating non-covalent interactions in crowded frameworks by 77Se and 125Te solid-state NMR Supramolecular Interactions of 1,2,5-Selenadiazole Derivatives Exploring new anionic selenium based pincer ligands Coordination and Reduction of 1,2,5-Telluradiazole Heterocycles Coordination Chemistry of Selenium- and Tellurium-Containing Pincer Ligands Novel reaction of 1,2,5-chalcogenadiazoles – coordination of anions by chalcogen atoms PCP-Bridged, Chalcogen-Centered Ligands: Coordination Chemistry and Redox Transformations Ferrocenyl Substituted 1,3-Dithiolanes via [3+2]-Cycloadditions of Thiocarbonyl S-Methanides with Ferrocenyl/Hetaryl Thioketones Synthesis and biological evaluation of new 5-aryl-4,5-dihydro1,3,4-thiadiazole analogues as small molecule antimicrobial agents In Search of Heavy Chalcogenido-d10-metallates Ionothermal Treatment of Chalcogenidometallates Probing Donor-Acceptor Interactions in peri-Substituted Diphenylphosphinoacenaphthyl-Element Dichlorides of Group 13 & 15 Elements Straightforward formation of the unprecedented 5-membered annulated ring containing the B-N moiety: 1H-2,1benzazaborolyl alkali metal salts, reactivity with electrophiles and redox behavior Catalytic Dehydrogenation of Amino Boranes – Formation of Condensed Borazine Compounds Titanocene-based Catalysts for Amine Borane Dehydrocoupling: Studies of the Mechanistic Role of Ti(III) Species and Formation of Polyaminoboranes 1,2-Azaborine, the BN derivative of ortho-benzyne Fragmentation vs. Dehydogenation of Borazines Cationic and Anionic Chains of only Lewis Base Stabilised Pnictogenylboranes Cooperative Al/P Lewis Pairs Based on Cationic Aluminium Complexes Binary Group 13/14 and 13/15 Zintl Anions and Their Reactions towards Ternary Intermetalloid Clusters Poster Contributions

Poster no P133

Presenter Eliza Leusmann

P134 P135

Derya Davarci Jatinder Singh

P136

Peter Bartoš

P137

Chen-Wei Liu

P138

Kamna Sharma

P139

Shabana Khan

P140 P141

Mehdi Elsayed Moussa Nanhai Singh

P142 P143

Hung Banh Kerstin Freitag

P144

Andrew Roberts

P145 P146

Isabell Nußbruch Katharina Dilchert

P147

Claudia Heindl

P148 P149 P150 P151 P152

Andrew Davies Maximilian Jost Francisco Miguel García-Valle Ferda Hacivelioglu Daniel Himmel

P153

Uttam Chakraborty

P154 P155 P156

Miriam Schwab Eric Maedl Dirk Herrmann

P157

Robert Wolf

Title of the Abstract Toward Connection of Aromatics and Ruthenium Complexes to Tin/Sulfur Clusters Ag(I) Coordination Polymers of Cyclophosphazenes Chiral Oxazoline Complexes of Basal Bulky Cobalt Sandwich Compounds and Cyclophosphazenes Luminescent complexes of copper(I) halides with functionalized tertiary phosphines Self-Assembly of a Luminescent Thiolato-Stabilized Hexanonacontanuclear Cuprous Wheel Hexanuclear and Tetranuclear Titanium Organophosphonates Formed via a Common Single-4-Ring Intermediate: Insights into Formation Pathways Structural Characterization and Luminescence Studies of Au(I) Complexes with PNP and PNB Based Ligand Systems A Bimetallic Phosphorous-Based Complex as a Building Block to Form Organometallic-Organic Hybrid Materials Synthesis, crystal structure and properties of ferrocenyl based pyridyl functionalized dithiocarbamate complexes of group 12 metals Ligand Protected Zinc Clusters Zinc-Zinc Interactions in Zinc Containing Complexes and Clusters Two Alternative Approaches to Access Mixed Hydride-Amido Zinc Complexes: Synthetic, Structural and Solution Implications Investigations on selenidozincates and –cadmates in ionic liquids Bottom-Up! Intermetallic Nickel Gallium Molecular Clusters and Complexes as Potential Precursors for Intermetallic Nanoparticles Incorporation of Small Molecules in Fullerene-like Supramolecules Rational molecular design: common-sense chemistry New ionic liquids containing the 2-Phosphaethynolate-anion Generation of a tripodal Schiff-base metalloligand Preparation of Conducting Pani Graft Polymers Methanol Synthesis in Silico.Quantumchmical Calculations on a Cu4Zn3O3 Picomodel Low valent Pentaaryl Cyclopentadienyl Fe, Co and Ni Complexes Reactions and characteristics of a cationic Ni(I)-Complex The reactivity of [(C10H15)Fe(η5-P5)] and [(C5H2tBu3)Ni(η3-P3)] Dinuclear Iron and Ruthenium Complexes Containing Naphthalene as a Bridging Ligand Transformations of Small Inorganic Molecules by Low-valent Transition Metalate Anions and Transition Metal Radicals

Poster Contributions

Poster no P158

Presenter Sandra Hitzel

P159

Iwao Omae

P160

Ulrike Kroesen

P161 P162 P163

Philipp Büschelberger Dominik Naglav Heiko Bauer

P164

Jürgen Pahl

P165

Laia Davin

P166

Lisa Vondung

P167

Michal Horni

P168 P169 P170

Mathies Evers María Fernández Millán Dietmar Glindemann

P171

Johannes Schläfer

P172

Corinna Hegemann

P173 P174

Tim Heidemann Aida Jamil

P175

Elif Okutan

Title of the Abstract Coordination chemistry of new di-/monoanionic ferrocene-based di-/phosphido chelate ligands Applications of the five-membered ring products of cyclometalation reactions as OLEDs Carbolithiation vs. Deprotonation: Control of the Reaction Behavior of Allylamines towards Alkyllithium Reagents Polyarene Metalates as Precatalysts for Hydrogenations: Scope and Mechanism Studies on heteroleptic Cp*Be-R compounds Calcium Hydride Catalyzed Highly 1,2-Selective Pyridine Hydrosilylation Synthesis and reactivity of an unprecedented cationic Mg βdiketiminate complex Regioselective deprotonation of N-heterocyclic molecules using ß-diketiminate stabilized magnesium bases Towards new concepts for bond activation using an iron-PBPpincer complex Trigonal to tetrahedral transitions in Cu(I) six-membered inorganic true heterocycles The Transmetalation Strategy to Heterometallic Gold Clusters Chiral Potassium Derivatives bearing Ligands of Natural Origin PTFE (“Teflon”) Sealing Ring for greaseless conical Glass Joint and for All-Glass-Syringe Synthesis of Functional Inorganic Materials starting from Metal Alkoxide and Metal Thiolate Precursors Precursor Synthesis for the Generation of Fluorine-dope SnO2 Nanomaterials Exploring the Chemistry of Ternary Heterometallic Alkoxides Ligand-Modulated Chemical and Structural Implications in Aluminum Heteroaryl Alkenolates BODIPY-Cyclophosphazene-Fullerene Triad as Heavy Atom Free Organic Triplet Photosensitizer

Poster Contributions

Plenary Lectures

Template Ring Approaches to Metallation Chemistry Robert E. Mulvey [email protected] Pure & Applied Chemistry, University of Strathclyde 295 Cathedral Street, Glasgow G1 1XL, Scotland, UK An indispensable tool in every synthetic chemist’s toolbox, metallation is used routinely in academia and industry to transform inert, synthetically intractable C-H bonds into reactive, synthetically tractable C-metal bonds. The seminal concept to date in the metallation of aromatic compounds has been directed ortho-metallation,[1] which is controlled predominately by the electron-accepting or -donating properties of the substituent coupled with its Lewis basicity. This presentation will demonstrate that mixed-metal ligand template structures[2] can be built that operating through special synergistic effects between their various components can perform metallation reactions outside the scope of conventional organolithium or lithium amide bases. Fitting perfectly with the theme of IRIS, examples are given of inorganic (mixedmetal amide) ring structures (so called pre-inverse-crowns[3]) that act as templates for deprotonation reactions unique in reactivity and selectivity, leading in the best cases to products (inverse crowns) in which ortho-metallation effects of substituents have been overridden by the template structure of the base.

Figure 1. Template base structure of a potassium-magnesium alkyl-amido pre-inverse-crown.

Acknowledgements: UK EPSRC and the Royal Society (Wolfson Merit Award) are thanked for their generous sponsorship. References: [1] M. C. Whisler, S. MacNeil, V. Snieckus, P. Beak, Angew. Chem. Int. Ed. 2004, 43, 2206. [2] A. J. Martínez-Martínez, A. R. Kennedy, R. E. Mulvey, C T. O ’Hara, Science 2014, 346, 834. [3] D. R. Armstrong, B. Conway, B. J. Fleming, J. Klett, A. J. Martínez-Martínez, A. R. Kennedy, R. E. Mulvey, S. D. Robertson, C T. O’Hara, Chem. Sci. 2014, 5, 771.

Plenary lecture - PL01

Evolving the Coordination Chemistry of p-Block Element Lewis Acceptors Neil Burford*, Saurabh S. Chitnis, Paul A. Gray and Alasdair P.M. Robertson [email protected] Department of Chemmistry University of Victoria, P.O. Box 3065, Stn CSC, Victoria, British Columbia, V8W 3V6, Canada We have recently demonstrated that homoatomic coordination chemistry offers a versatile approach to P-P bond formation, and a variety of synthetic methods are now available. Extrapolation of coordination chemistry to other p-Block element acceptor centers provides new approaches for general non-metal element-element bond formation. More importantly, in the context of the coordination chemistry of the transition metals, a potentially diverse and extensive coordination chemistry for nonmetal element acceptors is emerging for the tetraels (E = Si, Ge, Sn) and the pnictogens (Pn = P, As, Sb, Bi), as illustrated (L = neutral ligand, X = halogen) below. The synthesis, structure, bonding and reactivity for new complexes involving non-metal acceptors with classical ligands will be described.

Figure 1. Coordination drawings.

Acknowledgements: Natural Sciences and Engineering Research Council of Canada for funding. References: Angew. Chem. Int. Ed., 2011, 50, 11474; 2012, 51, 2964; 2013, 52, 2042; 2013, 52, 4863; 2014, 53, 6050 (review); 2014, 53, 3480. J. Am. Chem. Soc., 2014, 136, 12498; 2014, 136, 14941. Chem. Commun., 2011, 47, 12331; 2012, 48, 7922; 2012, 48, 7359; 2014, 50, 7979. Dalton, 2015, 44, 17 (review). Chem. Sci., 2015, 6, 2559.

Plenary lecture - PL02

Phosphorus-Containing Ring Systems from Low to High Oxidation States Christopher C. Cummins [email protected] Massachusetts Institute of Technology Cambridge, MA 02139 The book Nonexistent Compounds by W. E. Dasent gives consideration to compounds "... whose structures do not offend the simpler rules of valence, but which nevertheless are characterized by a low degree of stability." One such compound mentioned in the book is the diatomic molecule P2. The presentation will delineate synthetic access to sources of P2 that may be regarded (depending upon mechanism) as thermal molecular precursors to P2 or as P2 transfer agents. Also to be described are efforts to characterize volatilized species by molecular beam mass spectrometry and by spectroscopy. Reactivity studies involving P2that lead to new inorganic ring systems have been targeted, and these will be described with an eye to electronic structure elucidation of the reaction products. Inorganic ring systems based on new metaphosphate acid salt starting materials will be described as well, and here, an emphasis is placed on understanding the ramifications and applications of weak-field polyanions in coordination chemistry.

Plenary lecture - PL03

FLP-rings: Applications in Synthesis and Catalysis Doug Stephan [email protected] Department of Chemistry, University of Toronto 80 St George St Main group Lewis acids and bases are used in combination to activate hydrogen in frustrated Lewis pairs (FLPs). This concept has allowed the development of metalfree routes to novel reactivity and catalysis. In this lecture, we will describe a number of examples that demonstrate the utility of FLP-ring and Lewis acid systems in the synthesis of novel reagents, materials, polymers and catalysts. For example, FLPrings systems have been used to stabilize the otherwise unstable molecule SO. New approaches to Te-B electronic materials and polymers have been developed. In addition, novel Lewis acid catalysts have been designed based on electrophilic phosphorus based systems are discussed and shown to be effective for C-F bond hydrodefluorination catalysis, hydrosilylations, and hydrogenations. The implications of these findings for applications of main group species in materials chemistry and catalysis is considered in this lecture.

Acknowledgements: NSERC of Canada References: L.E. Longobardi, V. Wolter, D.W. Stephan, Angew. Chem. Int. Ed. 2015,54, 809-812. F.A. Tsao, D.W Stephan, Dalton Trans. 2015, 44 (1), 71-74. F.A. Tsao, D.W Stephan, Chem. Commun. 2015,51, 4287–4289. M.H. Holthausen, R.R. Hiranandani, D.W. Stephan, Chem. Sci. 2015, 6, 2016-2021. J.M. Farrell, D.W. Stephan, Angew. Chem. Int. Ed. 2015, doi.org/10.1002/ange.201500198

Plenary lecture - PL04

New Phosphorus-Heterocycles from simple Building Blocks Riccardo Suter, Dominikus Heift, Xiaodan Chen, Zoltan Benkö, Hansjörg Grützmacher * [email protected] Department of Chemistry and Applied Biosciences ETH Zurich Vladimir-Prelog-Weg 1 8093 Zürich Switzerland Sodium phosphaethynolate is easily prepared from sodium, phosphorus, a tertiary alcohol and a carbonate in a one-pot reaction.[1] It is best described by the resonance structures -O-C≡P (A) and O=C=P- (B) and serves as building block for a variety of phosphorus heterocycles with one, two, or three phosphorus centers (Figure 1).[2] In some reactions, classical cycloadditions to the C≡P triple bond occur while in others OCP- serves as a “P-” transfer reagent under loss of CO. Some of the newly prepared heterocycles show remarkable properties such as strong absorptions in the visible range of light. Furthermore, because all heterocycles obtained from OCP- are anionic, they serve themselves as valuable building blocks for organophosphorus compounds and transition metal complexes.[3] The syntheses of these species will be discussed and some insight into the reaction mechanisms obtained from NMR spectroscopy on intermediates combined with DFT computations will be given.

Figure 1: Various phosphorus heterocycles obtained from Na(OCP).

Acknowledgements: Funding by the ETH Zürich and Swiss National Science Foundation is gratefully achnowledged References: [1] D. Heift, Z. Benkö, H. Grützmacher, Dalton Trans. 2014, 43, 5920-5928. [2] D. Heift, Z. Benkö, H. Grützmacher, Chem. Eur. J. 2014, 20, 11326-11330. [3] R. Suter, unpublished results.

Plenary lecture - PL05

Lewis Acidic Properties of Organoantimony Compounds: Applications in Anion Sensing and Catalysis François P. Gabbaï [email protected] Department of Chemistry, Texas A&M University College Station, Texas 77843, USA In this presentation, we will show that the oxidation of organo-antimony(III) derivatives provides access to Lewis acidic antimony(V) derivatives which can be used in a number of applications ranging from anion sensing to organic reaction catalysis. The first part of the presentation will be dedicated to the chemistry of Lewis basic bidendate distibines and their oxidative conversion into the corresponding distiboranes.[1] These distiboranes behave as bidendate Lewis acids and readily chelate anions such as the fluoride anion. In the second part of the presentation, we will describe how stibines of general formula R3Sb can be oxidized even when ligated to transition metal complexes (M). This oxidation induces the formation of a M→Sb interaction which results in a drastic increase in the Lewis acidity of metal center.[2-4] Using a family of gold stibine derivatives, we will demonstrate that such coordinated stibine oxidation reactions can be used to afford potent hydroamination catalysts.

Figure 1. Example of a bidentate Lewis acidic fluoride receptor obtained by oxidation of the corresponding distibine.

Acknowledgements: This work was supported by the National Science Foundation (CHE-1300371), the Welch Foundation (A–1423) and Texas A&M University (Arthur E. Martell Chair of Chemistry) References: [1] M. Hirai, F. P. Gabbaï, Angew. Chem. Int. Ed. 2015, 54, 1205-1209. [2] C. R. Wade, F. P. Gabbaï, Angew. Chem. Int. Ed. 2011, 50, 7369-7372. [3] H. ang, T.-P. in, F. P. Gabba , Organometallics 2014, 33, 4368-4373. [4] J. S. Jones, C. R. Wade, F. P. Gabbaï, Angew. Chem. Int. Ed. 2014, 53, 8876-8879.

Plenary lecture - PL06

Group-14 element rich cages and rings as precursors and intermediates for the formation of intermetalloid clusters Thomas F. Fässler [email protected] Department of Chemistry Lichtenbergstrasse 4, D-85747 Garching Homoatomic frameworks, rings and cages frequently appear in intermetallic compounds that are composed of p-block (semi)metals in combination with an electropositive metal. Prominent examples of so-called Zintl phases are alkali-metal tetrel phases that among others contain five membered Si5 rings, tetrahedral E4 units or deltahedral E9 clusters (E = Si, Ge, Sn and Pb). Despite the fact that those Zintl phases are known since a long time only a limited number is eligible for transferring these units to soluble tetrel-rich molecular anions (Zintl anions). In recent years, however, the chemistry of Zintl ions has emerged and developed to a fast-growing field and has now provided a rich plethora of new compounds, including oxidative coupling reactions leading to dimers, oligomers, or polymers, addition of organic ligands, or by the inclu-sion of metal atoms under formation of endohedral (intermetalloid) cluster species and many of them disclosing non-classical bonds . [1] Remarkably, the major part of all reactions with organometallic precursors in solution reported so far involve transition metal complexes with late d block metals (Group 6 to Group 12). We will discuss recent results arising from our investigations into the reac-tivity of low-valent tetrel compounds with early transition metals such as titanium.[2]

Figure 1. Examples of intermetalloids with an emphasis on three- or five-membered En rings.

References: [1] a) S. Scharfe, F. Kraus, S. Stegmaier, A. Schier, T. F. Fässler, Angew. Chem. Int. Ed. 2011, 50, 3630; b) T. F. Fässler (Ed.), Zintl Ions: Principles and Recent Developments, Structure and Bonding, Springer-Verlag: Heidelberg, 2011; c) M. M. Bentlohner, W. Klein, Z. H. Fard, L.-A. Jantke, T. F. Fässler, Angew. Chem. Int. Ed. 2015, DOI: 10.1002/anie.201410199; d) M. Waibel, F. Kraus, S. Scharfe, T. F. Fässler, Angew. Chem. Int. Ed. 2010, 49, 6611; e) J.-Q. Wang, S. Stegmaier, B. Wahl, T. F. Fässler, Chem. Eur. J. 2010, 16, 1793; f) L. Yong, S .D. Hoffmann, T. F. Fässler, S. Riedel, M. Kaupp, Angew. Chem. Int. Ed. Engl. 2005, 44, 2092. [2] C. B. Benda, M. Waibel, T. F. Fässler, Angew. Chem. Int. Ed. 2015, 54, 522.

Plenary lecture - PL07

Novel approaches to E-H bond activation and functionalization using Main Group systems Simon Aldridge [email protected] Department of Chemistry, Oxford University Inorganic Chemistry Laboratory, South ParksRoad, Oxford, OX1 3QR, UK E-H bond activation processes represent key mechanistic steps in numerous catalytic reactions of key industrial importance. Classically such activation is brought about via oxidative addition utilizing the readily accessible n/n+2 redox states of ‘noble’ transition metals. Of late, economic and environmental imperatives have driven the development of alternative catalysts, including systems based on either (i) cooperative metal/ligand activation processes; and/or (ii) redox processes at a single (non-noble) metal site. In recent work we have been examining both approaches, and present recent results involving the activation and functionalization of H-H and N-H bonds.1,2 In terms of cooperative reactivity, ambiphilic systems capable of the activation of protic, hydridic and apolar H-X bonds across a Group 13 metal/activated bdiketiminato (Nacnac) ligand framework have been developed. Related hydride complexes derived from the activation of H2 can be shown to be competent catalysts for the highly selective reduction of CO2 to a methanol derivative.1 In terms of redox chemistry, bond modifying processes have been developed for group 14 metals. The oxidative addition of H2 as well as both protic and hydridic E-H bonds (N-H/O-H, SiH/B-H, respectively) to Sn(II) can be driven by employing strongly s-donating boryl ancillary ligands. In the case of ammonia and water, E-H oxidative addition can be shown to be followed by reductive elimination to give an N- (or O-) borylated product. Thus, in stoichiometric fashion at least, redox-based bond cleavage/formation is demonstrated for a single Main Group metal centre.

Figure 1. Oxidative addition and reductive elimination at Sn(II).

Acknowledgements: EPSRC (grants EP/L025000/1 and EP/K014714/1). References: 1. J.A.B. Abdalla, I.M. Riddlestone, R. Tirfoin, S Aldridge, Angew. Chem., Int. Ed., 2015, in press. DOI: 10.1002/anie.201500570. 2. A.V. Protchenko, J.I. Bates, L. Saleh, M.P. Blake, A.D. Schwarz, E. Kolychev, A.L. Thompson, C. Jones, P. Mountford, S. Aldridge, submitted.

Plenary lecture - PL08

Keynote Lectures

Cyclic and Acyclic Boron-based Chromophores: Highly Unusual Donor-Acceptor Systems Holger Braunschweig [email protected] University of Würzburg Am Hubland D-97074 Würzburg The incorporation of boron-based chromophores – most commonly electron-deficient acceptor (A) units – into p-conjugated systems, has spurred significant interest over the past 15 years due to the potential of such systems for applications in organic electronics. We have contributed a variety of boron-based heterocycles – that is aromatic borirenes and azaborinines as well as antiaromatic boroles – as cyclic building blocks for extended π-conjugated systems. More recently we have also developed a series of unprecedented electron-rich boron-based chromophores based on B-B double and triple bonds. Here, new synthetic approaches – both stoichiometric and catalytic - to such systems will be presented together with a survey of the highly unusual electronic and photophysical properties of particularly substituted diborenes.

Acknowledgements: We thank DFG and ERC for financial support References: [1] P. Bissinger, A. Steffen, A. Vargas, R. D. D. Dewhurst, A. Damme, H. Braunschweig Angew. Chem. 2015, 127, DOI: 10.1002/anie.201408993. [2] P. Bissinger, H. Braunschweig, A. Damme, C. Hörl, I. Krummenacher, T. Kupfer Angew. Chem. Int. Ed. 2015, 54, 359–362. [3] H. Braunschweig, M. A. Celik, F. Hupp, I. Krummenacher, L. Mailänder Angew. Chem. Int. Ed. 2015, 54, accepted. [4] H. Braunschweig, K. Geetharani, J. O. C. Jimenez-Halla, M. Schäfer Angew. Chem. Int. Ed. 2014, 53, 3500–3504. [5] J. Böhnke, H. Braunschweig, P. Constantinidis, T. Dellermann, W. C. Ewing, I. Fischer, K. Hammond, F. Hupp, J. Mies, H.-C. Schmitt, A. Vargas J. Am. Chem. Soc. 2015, 137, 1766–1769. [6] H. Braunschweig, R. D. Dewhurst, K. Hammond, J. Mies, A. Vargas, K. Radacki Science 2012, 336, 1420–1422.

Keynote lecture - KL01

Activation of Small Molecules by Biradicaloids Axel Schulz [email protected] Institut für Chemie, Universität Rostock Albert-Einstein-Str. 3a, 18059 Rostock, Germany This lecture deals with the synthesis and full characterization of biradicaloids of the type [E(m-NTer)]2 (E = element of group 15, Scheme 1 species 2).[1-3] The reactivity of these biradicaloids 2 was employed to activate small molecules bearing single, double and triple bonds (Scheme 1). Addition of chalcogens (O2 , S8 , Sex and Tex ) led to the formation of dichalcogen bridged E2N2 heterocycles. In formal [2πe+2πe] addition reactions small unsaturated compounds such as ethylene, acetylene, acetone, acetonitrile, tolane, diphenylcarbodiimide, and bis(trimethylsilyl)sulfurdiimide are readily added to the E2N2 heterocycle of the biradicaloid 2 yielding novel heteroatomic cage compounds. The reaction with CO and isonitriles led to the formation of new cyclic 5-membered heterocycles featuring also biradical character. Oxidation with silver salts gave stable cyclic radical cations (3+).

Scheme 1. Activation of small molecules by biradicaloids.

References: [1] A. Hinz, R. Kuzora, A. Schulz, A. Villinger, Chem. Eur. J. 2014, 20, 14659 – 16673. [2] A. Hinz, A. Schulz, A. Villinger, Angew. Chem. Int. Ed. 2015, 54, 668 – 672. [3] A. Hinz, A. Schulz, A. Villinger, Angew. Chem. Int. Ed. 2015, 54, 2776 – 2779.

Keynote lecture - KL02

Boron-Cations and Radicals Stabilized by Strong P→B Interactions M. Devillard, A. Rosenthal, G. Bouhadir, D. Bourissou [email protected] Laboratoire Hétérochimie Fondamentale et Appliquée Paul Sabatier University, 118 route de Narbonne, 31062 Toulouse, France Our group is interested in cooperative phenomena arising from ambiphilic compounds. In this presentation, our recent studies on naphthyl-bridged phosphorusboron derivatives will be presented. The three following sub-topics will be discussed: - Phosphine-boranes featuring strong, yet Lewis acid-responsive P→B interactions,[1] - Phosphine-stabilized borenium salts featuring versatile reactivity,[2] - Phosphine-stabilized boryl radicals: their electronic structure and chemical behavior.

Figure 1. Schematic representation of the naphthyl-bridged P/B derivatives

Acknowledgements: The CNRS, the Université Paul Sabatier and the Agence Nationale de la Recherche are acknowledged for financial support of this work. We thank Dr. K. Miqueu (Université de Pau et des Pays de l’Adour) for DFT calculations. References: [1] Bontemps, S.; Devillard, M.; Mallet-Ladeira, S.; Bouhadir, G.; Miqueu, K.; Bourissou, D. Inorg. Chem. 2013, 52, 4714. [2] Devillard, M.; Mallet-Ladeira, S.; Miqueu, K.; Bouhadir, G.; Bourissou, D. Angew. Chem. Int. Ed. 2015, DOI: 10.1002/anie.201500959.

Keynote lecture - KL03

New main group-metal-mediated strategies for ring functionalisation Eva Hevia [email protected] WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, G1 1XL, Glasgow, UK Recent advances have established that cooperative characteristics can be instilled into main group bimetallic systems by combining two different metals with distinct bond polarities within the same compound. The outcome of this cooperativity is that the bimetallic is capable of delivering new chemistry irreproducible by either of its single-metal components. Despite many synthetic organic studies having utilised these reagents, the key factors governing their reactions and cooperative behaviour still remain to be elucidated and fully understood.[1] To complement these organicfocused studies and gain a better understanding of this intriguing area, we have approached it from an alternative inorganic/structural/metal perspective. This presentation will highlight our recent results that provide valuable insights into the often blurred identities of the organometallic intermediates involved in key reactions such as deprotonation,[2] metal-halogen exchange and Pd-catalysed cross-coupling .[3] The first catalytic applications of these multicomponent reagents will also be discussed focussing on hydroamination reactions of unsaturated organic molecules such as isocyanates and olefins.[4] The opening applications of mixed ammoniummagnesiate salts in Green Chemistry will also be revealed through addition reactions of Grignard reagents to ketones under air and at room temperature using Deep Eutectic Solvents.[5]

References: [1] F. Mongin, A. Harrison-Marchand, Chem. Rev. 2013, 113, 7563. [2] (a) S. E. Baillie, T. D. Bluemke, W. Clegg, A. R. Kennedy, J. Klett, L. Russo, M. de Tullio, E. Hevia Chem. Commun. 2014, 50, 12859. (b) D. R. Armstrong, S. E. Baillie, V. L. Blair, N. G. Chabloz, J. Diez, J. Garcia-Alvarez, A. R. Kennedy, S. D. Robertson, E. Hevia, Chem. Sci. 2013, 4, 4259. [3] T. D. Bluemke, W. Clegg, P. García-Alvarez, A. R. Kennedy, K. Koszinowski, M. D. McCall, L. Russo, E. Hevia, Chem. Sci., 2014, 5, 3552. [4] A. Hernán-Gómez, T. D. Bradley, A. R. Kennedy, Z. L. Livingstone, S. D. Robertson, E. Hevia, Chem. Commun. 2013, 49, 8659. [5] C. Vidal, J. Garcia-Alvarez, A. Hernan-Gomez, A. R. Kennedy, E. Hevia, Angew. Chem. Int. Ed. 2014, 53, 5969

Keynote lecture - KL04

Nucleophilic boron derivatives, stable phosphinidenes and other main group species Guy Bertrand [email protected] UCSD/CNRS Joint Research Chemistry Laboratory University of California San Diego, La Jolla, CA, 92093-0343 In the first part of the lecture we will present results dealing with the preparation and reactivity of neutral and anionic boron derivatives.1 Then we will show that electrophilic carbenes, such as cyclic (alkyl)(amino)carbenes and pyramidalized NHCs can stabilize a variety of main group species in different oxidation states.2 The last part of the lecture will be devoted to the synthesis, reactivity and coordination behavior of the first stable phosphino nitrenes (nitrido-phosphorus)3 and phosphinidenes.4

References: 1 D. A. Ruiz, G. Ung, M. Melaimi, G. Bertrand, Angew. Chem. Int. Ed. 2013, 52, 7590-7592. 2 R. Kretschmer, D. A. Ruiz, C. E. Moore, A. L. Rheingold, G. Bertrand, Angew. Chem. Int. Ed. 2014, 53, 8176-8179. 3 F. Dielmann, D. M. Andrada, G. Frenking, G. Bertrand,J. Am. Chem. Soc. 2014, 136, 3800-3802. 4 L. Liu, D. Ruiz, G. Bertrand, Unpublished results

Keynote lecture - KL05

Base-Induced Isomerization of Unsaturated Group 14 Ring Systems Michael J. Cowley, Anukul Jana, David Nieder, Kai Abersfelder, and David Scheschkewitz* [email protected] Krupp-Chair of General and Inorganic Chemistry, Saarland University D-66125 S The coordination of Lewis bases to unsaturated main group systems exerts a considerable stabilising effect. Various otherwise inaccessible structural motifs have been isolated as stable adducts with N-heterocyclic or cyclic alkyl amino carbenes.[1] The nature of this interaction is subject of an ongoing discussion, in particular with regards to the alternative descriptions of the bonding situation as either donoracceptor bond or ylidic charge-separated systems.[2] We argued that reversibility of coordination is at least a sufficient criterion for the presence of a donor-acceptor interaction.[3] The lecture will discuss our recent results regarding the interaction of unsaturated Group 14 ring systems with N-heterocyclic carbenes and silylenes in this light, with a focus on base-coordinated stable representatives of the Si2(EX)R3 manifold (Scheme 1, EX = SiR,[4] GeCl,[5] P, GePh, etc.; R = Tip = 2,4,6-iPr3C6H2). Isomerization pathways include ring closure and opening, as well as 1,2- and 1,3migration of functional groups. Exchange and sequestration reactions of Nheterocyclic carbenes under mild conditions support the notion of reversibility. Subtle changes in size and/or donor properties of the coordinated base allow for the isolation of various unsaturated isomers with often dramatically altered physical properties. In selected cases coordinated and uncoordinated species in solution even co-exist in equilibrium providing firm support for weak donor-acceptor interactions in these cases. The potential of the newly emerging toolbox of synthetic manipulations for the construction of extended systems in lowvalent main group chemistry will be discussed.

References: [1] Review: Y. Wang, G. H. Robinson, Inorg. Chem. 2014, 53, 11815. [2] (a) D. Himmel, I. Krossing, A. Schnepf, Angew. Chem. Int. Ed. 2014, 53, 370. (b) G. Frenking, Angew. Chem. Int. Ed. 2014, 53, 6040. (c) R. Köppe, H. Schnöckel, Chem. Sci. 2015, 6, 1199. [3] (a) A. Jana, V. Huch, H. S: Rzepa, D. Scheschkewitz, Angew. Chem. Int. Ed. 2015, 54, 289–292. (b) A. Jana, V. Huch, H. S. Rzepa, D. Scheschkewitz, Organometallics 2015, DOI: 10.1021/om501286g. [4] M. J. Cowley, V. Huch, H. S. Rzepa, D. Scheschkewitz, Nat. Chem. 2013, 5, 876. [5] A. Jana, V. Huch, D. Scheschkewitz, Angew. Chem. Int. Ed. 2013, 52, 12179.

Keynote lecture - KL06

Low oxidation state main group compounds: stabilisation strategies and transition metal-like reactivity Cameron Jones [email protected] School of Chemistry, Monash University PO Box 23, Melbourne, VIC, 3800, Australia Considerable progress has been made over the last decade towards the stabilisation of very low oxidation state p-block compounds with bulky ligands. In this lecture the development of a new class of extremely bulky monodentate amido ligands will be discussed, as will their use in the preparation of previously inaccessible, coordinatively unsaturated low oxidation state p-block metal complex types.[1] The facile "transition metal-like" reactivity of these compounds towards small molecule (e.g. H2, CO2, NH3 etc.) activations, and associated catalytic processes, will also be detailed.[2]

Acknowledgements: Australian Research Council, US Air Force References: 1. T.J. Hadlington, M. Hermann, J. Li, G. Frenking, C. Jones, Angew. Chem. Int. Ed., 2013, 52, 10199 2. T.J. Hadlington, M. Hermann, G. Frenking, C. Jones, C. J. Am. Chem. Soc. 2014, 136, 3028.

Keynote lecture - KL07

Boron Cations and Poly-dentate Divalent Group 14 Ligands Ching-Wen Chiu [email protected] Department of Chemistry, National Taiwan University No. 1, Sec. 4, Roosevelt Rd., Taipei, 10617, Taiwan Studies on organoboranes have shown that the introduction of positive charge at boron center greatly enhances the electron deficiency of the molecule. Although boron mono-cations have proved to be effective in Lewis acid promoted organic transformations, reactivity studies of boron poly-cations remain relatively limited. Recently, our group has shown that [η5-Cp*B-IMes]2+, a di-substituted boron dication, could be transformed into the corresponding carbene-stabilized borabenzene upon addition of superhydride.[1] To gain better insight into boron dication, a series of closely related boron mono- and di-cations are synthesized. Reactivity and electron deficiency of these boron cations will also be addressed. In addition to boron cations, our group are also interested in bridging type poly-dentate N-heterocyclic carbenes and metallylenes. To this end, we have achieved the isolation of multi-dentate NHC ligands via stepwise synthesis or through assembly process.[2] In addition, a series of triphenylene-based planar tritopic metallylene, including germylenes, stannylenes and plumbylenes, are prepared. Theoretical computation on the aggregation induced color change of N-phenyl tris-germylene is also discussed.

Acknowledgements: Ministry of Science and Technology of Taiwan References: [1] C.-T. Shen, Y.-H. Liu, S.-M. Peng, C.-W. Chiu, Angew. Chem. Int. Ed., 2013, 52, 13293. [2] (a) Y.-T. Wang, M.-T. Chang, G.-H. Lee, S.-M. Peng, C.-W. Chiu, Chem. Commun., 2013, 49, 7258; (b) J.-H. Su, G.-H. Lee, S.-M. Peng, C.-W. Chiu, Dalton Trans., 2014, 43, 3059; (c) Y.-H. Chen, K.-E. Peng, G.-H. Lee, S.-M. Peng, C.-W. Chiu, RSC Adv.,2014, 4, 62789.

Keynote lecture - KL08

From Metalloaromaticity to N-Heterocyclic Carbenes: The Evolution of Inorganic Rings Gregory H. Robinson* [email protected] Department of Chemistry, The University of Georgia Athens, Georgia 30602 USA Two decades ago we reported a compound containing a ring of three gallium atoms, Na2[GaR]3.[1] This organometallic compound, a 2π-electron system isoelectronic with the aromatic triphenylcyclopropenium cation, offered experimental realization of metalloaromaticity - the concept that a metallic ring system could exhibit traditional aromatic behavior. Recently, we initiated an effort to explore the main group chemistry of N-heterocyclic carbenes, and have prepared a number of interesting carbene-stabilized compounds - some of which contain novel three-membered rings such as P2B [2] and Si2O (below). Indeed, the recently reported compound containing the Si2O ring is a rare molecular example of a stabilized silicon oxide moiety. This talk will concern our most recent results in the synthesis of inorganic ring systems and place them in historical perspective with our earlier work.

References: [1] X.-W. Li., W. T. Pennington, G. H. Robinson J. Am. Chem. Soc., 1995, 117, 7578. [2] Y. Wang, Y. Xie, M. Y. Abraham, P. Wei, H. F. Schaefer III, P. v. R. Schleyer, G. H. Robinson Chem.Comm., 2011, 47, 9224.

Keynote lecture - KL09

Catalysis in Service of Main Group Chemistry: Metal-Mediated and Metal-Free Routes to Molecules and Materials based on Elements from Group 13-15 Ian Manners [email protected] School of Chemistry, University of Bristol Cantock's Close, Bristol, BS8 1TS, UK Although metal-catalyzed reactions have played a profound role in organic synthesis, catalytic routes to main group molecules and materials are much less explored.1 In this talk the use of catalytic processes to dehydrogenate group 13 – 15 Lewis acidLewis base adducts such as amine- and phosphine-boranes and related species will be discussed. In addition to mechanistic details, unexpected discoveries such as metalfree hydrogen exchange reactions will be described. The work has relevance to the synthesis of new polymeric (e.g. polyamino- and phosphinoboranes, analogs of polyolefins with a BN/BP backbone) and 2D materials and also to hydrogen storage and transfer chemistry. 2

References: 1. Leitao, E.M.; Jurca, T.; Manners, I. Nature Chem. 2013, 5, 857. 2. Schaefer, A.; Jurca, T. et al Angew. Chem. Int. Ed. 2015 in press.

Keynote lecture - KL10

Inorganic Heterocycles: From Light-emitting Entities to Surprising Products from Ligand Activation Eric Rivard, Gang He, Melanie W. Lui, William Torres Delgado, Olena Shynkaruk, S. M. Ibrahim Al-Rafia [email protected] Department of Chemistry, University of Alberta 11227 Saskatchewan Dr., Edmonton, Alberta, Canada, T6G 2G2 Our group has had a long standing interest in inorganic ring systems [1] with particular recent focus given to the development of tellurophenes which show rarely observed phosphorescence in the solid state in the presence of oxygen.[2,3] In addition, during our explorations of N-heterocyclic carbenes (NHCs) and N-heterocyclic olefins (NHOs) as donors to main group element species [4], we uncovered unusual ringexpansion/ligand activation processes involving these generally thought to be inert Lewis bases [5,6].

Acknowledgements: This research was supported by NSERC of Canada, Alberta InnovatesTechnology Futures and the Canada Foundation for Innovation References: [1] G. He, O. Shynkaruk, M. W. Lui, E. Rivard, Chem. Rev. 2014, 114, 7815. [2] G. He, E. Rivard et al. Angew. Chem., Int. Ed. 2014, 53, 4587. [3] G. He, E. Rivard et al. Chem. Commun. 2015, 51, 5444. [4] E. Rivard, Dalton Trans. 2014, 43, 8577 and references therein. [5] S. M. I. Al-Rafia, R. McDonald, M. J. Ferguson, E. Rivard, Chem. Eur. J. 2012, 18, 13810. [6] M. W. Lui, C. Merten, M. J. Ferguson, R. McDonald, Y. Xu, E. Rivard, Inorg. Chem. 2015, 54, 2040.

Keynote lecture - KL11

Main Group Strategy for Photo and Electronic Functions Shigehiro Yamaguchi [email protected] Institute of Transformative Bio-Molecules (WPI-ITbM), Nagoya University, Furo, Chikusa, Nagoya, 464-8602, Japan Incorporation of main group elements into -conjugated skeletons is a powerful strategy to develop new photo- or electro-functional molecules with unusual properties. Representative design principles are to make use of an orbital interaction between a  skeleton and a main group element moiety, or to utilize the coordination number change of a main group element. Based on these approaches, we have so far developed various types of electronic and sensory materials. In this lecture, we would like to discuss recent progress in our chemistry regarding the following two subjects. First, we have recently succeeded in the preparation of a series of model compounds for boron-doped graphenes, such as compound 1.[1] These compounds were obtained as a stable compound due to the structural constraint in an enforced planar fashion.[2] The detailed studies on their reactivity and properties demonstrate the potential utilities for this material class.[3] Second, we have also developed phosphoruscontaining fluorescence probes for bioimaging.[4] Incorporation of an electronwithdrawing phosphine oxide moiety into a -skeleton enables us to produce highly electron-accepting scaffolds, such as a phosphole P-oxide, which were employed by the combination with electron-donating groups to produce environment-sensitive fluorescent probes like 2.

References: [1] a) S. Saito, K. Matsuo, S. Yamaguchi, J. Am. Chem. Soc. 2012, 134, 9130. b) C. Dou, S. Saito, K. Matsuo, I. Hisaki, S. Yamaguchi, Angew. Chem. Int. Ed. 2012, 51, 12206. c) K. Matsuo, S. Saito, S. Yamaguchi, J. Am. Chem. Soc. 2014, 136, 12580. [2] Z. Zhou, A. Wakamiya, T. Kushida, S. Yamaguchi, J. Am. Chem. Soc. 2012, 134, 4529. [3] T. Kushida, A. Shuto, M. Yoshio, T. Kato, S. Yamaguchi, Angew. Chem. Int. Ed. 2015, in press. [4] E. Yamaguchi, C. Wang, A. Fukazawa, M. Taki, Y. Sato, T. Sasaki, M. Ueda, N. Sasaki, T. Higashiyama, S. Yamaguchi, Angew. Chem. Int. Ed. 2015, in press.

Keynote lecture - KL12

Ligand-Based Redox Chemistry with Aluminum(III) Louise A. Berben [email protected] Department of Chemistry, University of California 1 Shields Ave, Davis, CA 95616 This talk will describe the synthesis and characterization of a series of Al(III) complexes which are stabilized by iminopyridine-based ligands. As an example, I will describe the structure and reactivity of (PhI2P)AlCl and (PhI2P)AlH which both have square planar geometry around the aluminum center (PhI2P is a phenyl substituted tridentate bis(imino)pyridine ligand). The Al centers in these square planar molecules are Lewis acidic and coordinate bases such as phosphines, pyridine, and ethers to become five-coordinate. In the presence of weak acids such as alcohols (or amines), O-H (or N-H) bond activation is observed where the proton is transferred to the amido donor atom of the PhI2P ligand. The activation of these polar bonds leads to dehydrogenation of the substrates in the examples where the substrate has a beta C-H bond. In addition to this metal-ligand cooperative proton transfer chemistry, we have also explored ligand-based proton and electron transfer chemistry. Using (PhI2P)AlCl, the ligand can be protonated twice, and then reduced by two electrons to quantitatively generate H2 . Performed electrochemically, this reaction is catalytic in production of H2 via the ligand-based proton and electron transfer events.

Keynote lecture - KL13

Novel phosphorus-containing ring systems derived from the 2phosphaethynolate anion Jose M. Goicoechea* [email protected] Department of Chemistry, University of Oxford Chemistry Research Laboratory, 12 Mansfield Road, Oxford, OX1 3TA, U.K. The 2-phosphaethynolate anion (PCO−), first reported by Becker and co-workers,[1] can be readily accessed by carbonylation of the heptaphosphide trianion [P 7]3−.[2] This heavier cyanate analogue contains a reactive P−C multiple bond and can be employed as an ambidentate nucleophile or as a precursor to novel phosphorus-containing compounds.[3] For example, [2+2] cycloaddition reactions with heteroallenes (carbodiimides and isocyanates) give rise to four-membered rings containing a phosphide vertex.[1] Similarly, PCO− reacts with molecules with unsaturated maingroup element–element bonds also affording novel heteroatomic ring systems.[4] By analogy with Wöhler’s urea synthesis, direct reaction of PCO− with ammonium salts has been shown to yield phosphinecarboxamide (PH2C(O)NH2 ; Scheme 1), an airand moisture-stable primary phosphine.[5] This talk will focus on recent developments concerning the chemical reactivity of PCO− and PH2C(O)NH2 for the formation of novel neutral and anionic inorganic ring systems.

Figure 1. Synthesis of phosphinecarboxamide.

Acknowledgements: We thank the University of Oxford and the EPSRC (EP/K039954/1) for financial support. References: [1] G. Becker, W. Schwarz, N. Seidler, M. Westerhausen, Z. Anorg. Allg. Chem., 1992, 612, 72. [2] A. R. Jupp, J. M. Goicoechea, Angew. Chem., Int. Ed., 2013, 52, 10064. [3] See for example: (a) S. Alidori, D. Heift, G. Santiso-Quinones, Z. Benkő, H. Grützmacher, M. Caporali, L. Gonsalvi, A. Rossin, M. Peruzzini, Chem.−Eur. J., 2012, 18, 1 0 (b) . Chen, S. Alidori, F. F. Puschmann, G. Santiso-Quinones, Z. Benkő, Z. i, G. Becker, H.-F. Grützmacher, H. Grützmacher, Angew. Chem. Int. Ed., 2014, 53, 1 1 (c) D. Heift, Z. Benkő, H. Grützmacher, Angew. Chem. Int. Ed., 2014, 53, 7 7 (d) A. M. Tondreau, Z. Benkő, J. R. Harmer, H. Grützmacher, Chem. Sci. 2014, 5, 1545. [4] T. P. Robinson, M. J. Cowley, D. Scheschkewitz, J. M. Goicoechea, Angew. Chem., Int. Ed., 2015, 54, 683. [5] A. R. Jupp, J. M. Goicoechea, J. Am. Chem. Soc., 2013, 135, 19131.

Keynote lecture - KL14

Early Main Group Metal Hydride Complexes Sjoerd Harder* [email protected] Inorganic and Organometallic Chemistry, University Erlangen-Nürnberg Egerlandstrasse 1, 91058 Erlangen, Germany The enormous lattice energies for group 1 and 2 metal hydride salts, (MH)n and (MH2)n, make the syntheses and isolation of well-defined early main group metal hydride complexes a major challenge.[1] In here we present synthetic methods towards such metal hydride complexes, their use in catalysis[2] and their role as molecular models for hydrogen storage systems.[3]

References: [1] S. Harder, Chem. Commun. 2012, 48, 11165. [2] (a) S. Harder, Chem. Rev. 2010, 110, 3852. (b) A. G. M. Barrett, M. R. Crimmin, M.S. Hill, P. A. Procopiou, Proc. R. Soc. A 2010, 466, 927. (c) M. R. Crimmin, M. S. Hill, Topics in Organometallic Chemistry, Ed. S. Harder, 2013, 45, 191. [3] (a) S. Harder, J. Spielmann, J. Intemann, H. Bandmann, Angew. Chem. Int. Ed. Engl. 2011, 50, 4156. (b) J. Intemann, J. Spielmann, S. Harder, Chem. Eur. J. 2013,19, 8478.

Keynote lecture - KL15

Bermuda-Clusters…? On the Interaction of Chelating Bipyridines with Subvalent Gaand InSalts of the [Al(ORF)4]WCA. Ingo Krossing* [email protected] Institute for Inorganic and Analytical Chemistry, University of Freiburg Albertstr. 21, GER-79104, Freiburg When Ag+[Al(ORF)4]– and metallic gallium or indium are sonicated in aromatic solvents like fluorobenzene, a precipitate of silver metal and highly soluble M(C6H5F)n+ salts (M = Ga, In; n = 2, 3) with the weakly coordinating [Al(ORF)4]– anion are formed in a oxidative route in quantitative yield. These materials proved to be valuable for coordination chemistry with a wide range of classical ligands like phosphanes, crown ether, NHCs etc. By contrast, 2,2’‑bipyridine (bipy) triggers a disproportionation of the univalent gallium salt [Ga(C6H5F)2]+[Al(ORF)4]– (RF = C(CF3)3). In the resultant monomeric and paramagnetic [Ga(bipy)3]2+ complex, the gallium cation is coordinated in a distorted octahedral fashion by three bipy ligands. Excluding the formation of a gallium(II) species, the EPR and DFT investigations clearly assign a ligand‑centered radical: i.e., a [GaIII(bipy)2(bipy)●−]2+ complex. The application of the heavier homologue [In(C6H5F)2]+[Al(ORF)4]– astonishingly led to aggregation and we isolated the first cationic, homonuclear, three‑ and four‑ membered triangular (Bermuda-?)clusters of univalent indium: [In3(bipy)6]3+, [In3(bipy)5]3+ and [In4(bipy)6]4+ (Figure 1). Herein, the indium(I) cations are coordinated by one, 1.5 or two bipy ligands in a chelating, trigonal or tetragonal pyramidal fashion and form In−In bonded triangular and rhombic clusters. To our knowledge, the In−In distances (2 .1−2 9. pm) include the shortest that have been reported so far. DFT studies suggest a stepwise formation of the clusters, possibly via their triplet state, and Born‑Haber‑Cycle investigations attribute the overall driving force of the reactions to the high lattice enthalpies of the resultant MX3and MX4salts.

Figure 1. Molecular structures of Indium-bipyridine complexes, all balanced by the [Al(ORF)4]- WCA.

Keynote lecture - KL16

New Aspects in the Chemistry of Al-containing Cyclic Compounds Norihiro Tokitoh [email protected] Institute for Chemical Research, Kyoto University Gokasho, Uji, Kyoto 611-001, Japan Group 13 element heteroles potentially exhibit unique properties originating from the orbital interactions between the vacant p orbital of the group 13 elements and the π* orbitals of the butadiene moieties.1 However, reports on heavier group 13 heteroles, such as alumoles (1-alumacyclopenta-2,4-dienes), have been limited so far.2 Recently, we have reported the synthesis of the first stable Lewis-base free alumole 1 by using the bulky Mes* group (Mes* = 2,4,6-(t-Bu)3C6H2) (Scheme 1).3 In this presentation, synthesis and properties of a new type of alumole derivative, 1-bromoalumole 2, will be discussed.4 1-Bromoalumole 2 was obtained as a thermally-stable crystalline solid by the treatment of 4,5-diethyl-3,6-dilithio-3,5-octadiene (3) with AlBr3. In the solid state, 1-bromoalumole 2 forms a dimer owing to the coordination of the π(C=C) bond of one molecule of 2 to the vacant 3p(Al) orbital of another molecule of 2. Reactions of 2 with Mes*Li and LiN(SiMe3)2 afforded Mes*-substituted alumole 1 and 1aminoalumole–THF complex 4,5 respectively. Reactions of 2 with other reagents including alkynes will also be reported.

Scheme 1

References: [1] a) S. Yamaguchi, A. Wakamiya, Pure Appl. Chem. 2006, 78, 1413; b) H. Braunschweig, T. Kupfer, Chem. Commun. 2011, 47, 10903. [2] Important reports on alumoles: a) H. Hoberg, R. Kraus-Göing, J. Organomet. Chem. 1977, 127, C29; b) C. Krüger, J. C. Sekutowski, H. Hoberg, R. Kause-Göing, J. Organomet. Chem. 1977, 141, 141; c) H. Hoberg, W. Richter, J. Organomet. Chem. 1980, 195, 347. [3] T. Agou, T. Wasano, P. Jin, S. Nagase, N. Tokitoh, Angew. Chem. Int. Ed. 2013, 52, 10031. [4] T. Wasano, T. Agou, T. Sasamori, N. Tokitoh, Chem. Commun. 2014, 50, 8148. [5] T. Agou, T. Wasano, T. Sasamori, N. Tokitoh, Organometallics 2014, 33, 6963.

Keynote lecture - KL17

Oral Presentations

Main Group Elements as Transition Metals: Reactions of Phosphorus-Carbon Multiple Bonds with Small Molecules Rosalyn L. Falconer, Christopher A. Russell* [email protected] School of Chemistry, University of Bristol Cantock’s Close, Bristol, BS8 1TS, UK One of the key goals of modern main group chemistry is to mimic reactivity most commonly associated with the transition metals.[1] This challenge can be met by utilising both HOMO and LUMO orbitals on the main group molecule, which, when acting in concert, can lead to the activation of small molecules - this key concept underpins much of the important reactivity and applications of d-block chemistry. Several main group systems, for example, heavy p-block multiple bonds, Frustrated Lewis Pairs and contemporary carbene chemistry, are celebrated for demonstrating aspects of such reactivity. Herein we dicsuss the extension of this concept to phosphorus-carbon multiple bonds.[2] We will explore the reactivity of some specific examples of P/C multiple bonds in the activation of small molecules (for example, H2, alkenes, dienes, silanes, germanes) from both a synthetic and mechanistic viewpoint.

Acknowledgements: We acknowledge the Bristol Synthetic Chemistry Doctoral Training Centre for funding References: [1] P. P. Power, Nature 2010, 463, 171-177. [2] a) N. S. Townsend, M. Green, C. A. Russell, Organometallics 2012, 31, 2543-2545; b) N. S. Townsend, S. R. Shadbolt, M. Green, C. A. Russell, Angew. Chem. Int. Ed. 2013, 52, 3481-3484; c) L. E. Longobardi, C. A. Russell, M. Green, N. S. Townsend, K. Wang, A. J. Holmes, S. B. Duckett, J. E. McGrady, D. W. Stephan, J. Am. Chem. Soc. 2014, 136, 13453-13457.

Oral presentation - A01

The Addition-Isomerization Polymerization of Phosphaalkenes Shuai Wang, Andrew Priegert, Spencer Serin, Derek P. Gates* [email protected] Department of Chemistry, University of British Columbia 2036 Main Mall, Vancouver, BC, Canada, V6T 1Z1 The addition polymerization of olefins is perhaps the most widely used and general method for the preparation of commodity polymers. For the past decade, we have been investigating the extension of addition polymerization to the P=C bond of phosphaalkenes.1 In particular, we have reported that MesP=CPh2 may be polymerized using thermal, radical or anionic methods of initiation. The resultant polymers, poly(methylenephosphine)s (PMPs), represent a new class of functional phosphorus-containing macromolecule. Recently, we have discovered that the radical polymerization of MesP=CPh2 with alkoxyamine, Ph(Me)CH·TEMPO, follows an unprecedented addition-isomerization mechanism.2 The addition step appears to be followed by an unexpected H-atom transfer from the ortho-Me group of the Mes substituent. Thus, the microstructure of PMP is better represented by (1, x > y). This presentation will describe our latest mechanistic findings for the polymerization of MesP=CPh2 and related derivatives. Of particular focus will be the study of the anioninitiated polymerization including the stepwise addition to the P=C bond and the possibility of isomerization during the propagation. In addition, new directions in the synthesis of functional phosphine-containing polymers such as PMPs will be discussed.3

Acknowledgements: We thank NSERC of Canada for supporting this work. References: 1 For a review, see : Bates, J. I.; Dugal-Tessier, J.; Gates, D. P. Dalton Trans. 2010, 39, 3151. 2 Siu, P. W. ; Serin, S. C.; Krummenacher, I.; Hey, T. W.; Gates, D. P. Angew. Chem. Int. Ed. 2013, 52, 6967. 3 Rawe, B. W.; Chun, C. P.; Gates, D. P. Chem. Sci. 2014, 5, 4928; S. C. Serin, B. O. Patrick, G. R. Dake, D. P. Gates, Organometallics, 2014, 33, 7215.

Oral presentation - A02

Highly electron-rich phosphines for the activation of small molecules Fabian Dielmann [email protected] Department of Inorganic and Analytical Chemistry, University of Münster Corrensstrasse 30, GER-48149, Münster Owing to their strong σ-donor properties N-heterocyclic carbenes play an important role as ligands in transition metal catalysis as well as for the activation of small molecules. As part of our program to enhance the donor strength of phosphines we report a conceptually new approach based on the use of imidazol-2-ylidenamino groups directly attached to the phosphorus atom. The new phosphines depict excellent donor abilities, which can even exceed that of N-heterocyclic carbenes. Furthermore, the steric and electronic properties of the new ligands can be easily varied owing to the facile and modular synthesis. Our approach to highly electron-rich phosphines provides new perspectives for the development of transition metal catalysts and for the activation of small molecules.

Figure 1. Donor abilities of imidazol-2-ylidenaminophosphines

Oral presentation - A03

Synthesis and Reactivity of a Zwitterionic Diphosphanide Kai Schwedtmann, Felix Hennersdorf, Michael H. Holthausen, Jan J. Weigand* [email protected] Department of Chemistry and Food Chemistry, Dresden University of Technology Mommsenstrasse 4, GER-01062, Dresden The cage compound [DippP5Cl][GaCl4][1] (Dipp = 2,6-diisopropylphenyl) reacts with three equivalents of a NHC (N-heterocyclic carbene) via an unprecedented [3+2]fragmentation of the P5-core to give an imidazoliumyl-substituted P3+-cation and a zwitterionic diphosphanide (see chart).[2] The structure of this unusual zwitterionic diphosphanide is confirmed by NMR spectroscopy and X-ray diffraction analysis. Subsequent transformation reactions of diphosphanides give access to new, interesting phosphorus compounds such as imidazoliumyl-substituted cationic diphosphanes and diphosphenes.

Acknowledgements: This work was supported by the Fonds der Chemischen Industrie (FCI, Liebig scholarship for F.H. and M.H.H) and the German Science Foundation (DFG, WE 4621/2-1). References: [1] M. H. Holthausen, J. J. Weigand, Chem. Soc. Rev., 2014, 43, 6639 – 6657. [2] M. H. Holthausen, S. K. Surmiak, P. Jerabek, G. Frenking, J. J. Weigand, Angew. Chem. Int. Ed., 2013, 52, 11078 – 11082.

Oral presentation - A04

'Inorganic' Arylphosphines Jonathan A. Bailey, Hazel A. Sparkes, Paul G. Pringle* [email protected] School of Chemistry, University of Bristol Cantocks Close, Bristol BS8 1TS, UK Arylphosphines are a hugely important class of compounds whose applications in synthetic chemistry range from stoichiometric organic synthesis to coordination chemistry and homogeneous catalysis. We are interested in the synthesis of arylphosphines in which C2 fragments of the aryl ring have been formally replaced with isoelectronic BN fragments.[1] In this presentation, the preparation and chemistry of borylphosphines of the type 1-3 shown in Figure 1 will be discussed. In particular, the remarkably specific insertion of oxygen into the P-B bonds to give P-O-B systems will be rationalised. Compounds 1-3 behave as electron-rich ligands to late transition metals to give complexes with applications in homogeneous catalysis. Recently we have succeeded in making triborazinylphosphine 3c or "inorganic triphenylphosphine". Similarities and differences between the chemistry of 3c and triphenylphosphine will be discussed.

Figure 1. Azaborinylphosphines: 'inorganic' analogues of arylphosphines.

Acknowledgements: We thank the European Union (Marie Curie ITN SusPhos, Grant Agreement No. 317404) for financial support. References: [1] (a) J. A. Bailey, H. A. Sparkes, P. G. Pringle, Chem. Eur. J., 2015, 21, 5360. (b) J. A. Bailey, M. Ploeger, P. G. Pringle, Inorg. Chem., 2014, 53, 7763. (c) J. A. Bailey, M. F. Haddow, P. G. Pringle, Chem. Commun., 2014, 50, 1432.

Oral presentation - A05

An Al/P Based Frustrated Lewis Pair as an Efficient Ambiphilic Ligand for the Coordination and Activation of Polar Compounds Philipp Wegener, Agnes Wollschläger, Werner Uhl* [email protected] Institut für Anorganische und Analytische Chemie, Universität Münster Corrensstrasse 30, GER 48149 Münster The Al/P based frustrated Lewis pair 1 is obtained by hydroalumination of the corresponding alkynylphosphine.[1] It is an excellent starting compound for the activation of various substrates and an efficient ambiphilic ligand for the coordination of a wide variety of bifunctional atoms or molecules. The reaction with azides led to the formation of adducts (2) which featured four-membered AlCPN heterocycles and azide groups in terminal position. Heating of 2 resulted in release of nitrogen and the formation of nitrene adducts 3 in which the electron sextet species nitrene is captured by coordination to the Lewis basic phosphorus and Lewis acidic aluminium atoms. Compound 4 represents the bifunctional stabilization of monomeric gallium hydride. It has a mixed metal Ga-H-Al 3c-2e bond and was obtained by treatment of 1 with GaH3×NMe2Et. Boron trihalides yielded adducts (5) with the boron atoms bonded to phosphorus and one halogen atom in the bridging position between aluminum and boron atoms. Rearrangement was observed for the compounds of the heavier halogens resulting in the formation of B-H species via β-hydrogen elimination and intermediate borenium cations.[2] Electron sextet chalcogen atoms were coordinated to yield AlCPY heterocycles (Y = O, S, Se, Te). The P-Te moiety in 6 is stabilized by coordination to the Lewis acidic aluminium atom, and a remarkable dimer is formed in the solid state as a result of Te-Te interactions.

Figure 1.

References: [1] C. Appelt, W. Uhl, et al. Angew. Chem. Int. Ed. 2011, 50, 3925. [2] W. Uhl, C. Appelt, A. Wollschläger, A. Hepp, Inorg. Chem. 2014, 53, 8991.

Oral presentation - A06

Cooperative Lewis Acid/Base Catalysis Devin Boom, Emmanuel Nicolas, Johan de Boed, Andreas W. Ehlers, J. Chris Slootweg* [email protected] Department of Chemistry and Pharmaceutical Sciences, VU University Amsterdam De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands The discovery of single-bond activation at transition-metal centers has led to a plethora of catalytic transformations, which highlights the power of organometallic chemistry. Recently, main-group systems, such as group 15/13-based frustrated Lewis pairs (FLPs), possessing a lone pair of electrons and a vacant orbital were also shown to be able to catalytically activate chemical bonds.[1] As substrate, amine-boranes have gained a lot of attention as potential hydrogen storage materials, and a variety of transition metal complexes were reported as efficient dehydrogenation catalysts.[2] However, the number of TM-free reagents is very limited and only a few systems were reported to be catalytically active.[3] In this presentation, we describe the dehydrogenation of amine-boranes using cooperative Lewis acid/base catalysis with different pre-organized frustrated Lewis pairs.[4] In addition, a „rational catalyst design“ approach to optimize this catalytic process will be presented and the impact of this discovery for other acceptorless dehydrogenation reactions will be illustrated.[5]

Figure 1. Rational catalyst design for the metal-free dehydrogenation of amine-boranes.

References: [1] D.W. Stephan, Acc. Chem. Res. 2015, 48, 306. [2] G. Alcaraz, S. Sabo-Etienne, Angew. Chem. Int. Ed. 2010, 49, 7170. [3] C. Appelt, J.C. Slootweg, K. Lammertsma, W. Uhl, Angew. Chem. Int. Ed. 2013, 52, 4256. [4] J.C. Slootweg, K. Lammertsma, et al. J. Am. Chem. Soc. 2012, 134, 201. [5] C. Gunanathan, D. Milstein, Science 2013, 341, 249.

Oral presentation - A07

Boron-Cations and Radicals Stabilized by Strong P→B Interactions M. Devillard, A. Rosenthal, G. Bouhadir, D. Bourissou [email protected] Laboratoire Hétérochimie Fondamentale et Appliquée Paul Sabatier University, 118 route de Narbonne, 31062 Toulouse, France Our group is interested in cooperative phenomena arising from ambiphilic compounds. In this presentation, our recent studies on naphthyl-bridged phosphorusboron derivatives will be presented. The three following sub-topics will be discussed: - Phosphine-boranes featuring strong, yet Lewis acid-responsive P→B interactions,[1] - Phosphine-stabilized borenium salts featuring versatile reactivity,[2] - Phosphine-stabilized boryl radicals: their electronic structure and chemical behavior.

Figure 1. Schematic representation of the naphthyl-bridged P/B derivatives

Acknowledgements: The CNRS, the Université Paul Sabatier and the Agence Nationale de la Recherche are acknowledged for financial support of this work. We thank Dr. K. Miqueu (Université de Pau et des Pays de l’Adour) for DFT calculations. References: [1] Bontemps, S.; Devillard, M.; Mallet-Ladeira, S.; Bouhadir, G.; Miqueu, K.; Bourissou, D. Inorg. Chem. 2013, 52, 4714. [2] Devillard, M.; Mallet-Ladeira, S.; Miqueu, K.; Bouhadir, G.; Bourissou, D. Angew. Chem. Int. Ed. 2015, DOI: 10.1002/anie.201500959.

Oral presentation - A08

Activation of π-Bonds Towards Cyclization Reactions using Lewis Acidic Boranes Rebecca L. Melen* [email protected] School of Chemistry, Cardiff University Main Building, Park Place, Cardiff, CF10 3AT, UK Depletion of the π-electron density in alkenes and alkynes, by Lewis-acid (electrophile) coordination, activates such groups to nucleophilic attack from amines, phosphines, thiols, amides and/or other C-C π-bonds. In these reactions the Lewis acid and Lewis base (nucleophile) undergo a 1,2-addition across the π-bond, reactivity that has been observed in frustrated Lewis pair (FLP) chemistry.[1] Recently we have established that main group ewis acids are capable of activating C≡C π-bonds bearing intramolecular nucleophiles towards cyclization reactions yielding a diversity of heterocycles containing B, N and O heteroatoms (Figure 1).[2-3] In some cases these heterocycles can be formed catalytically in the absence of a transition metal. [2] Recent developments will be discussed.

Figure 1. Cyclization reactions using boron Lewis acids.

References: [1] R. L. Melen Chem. Commun., 2014, 50, 1161. [2] R. L. Melen, M. M. Hansmann, A. J. Lough, A. S. K. Hashmi, D. W. Stephan Chem.-Eur. J. 2013, 19, 11928. [3] M. M. Hansmann, R. L. Melen, F. Rominger, A. S. K. Hashmi, D. W. Stephan J. Am. Chem. Soc. 2014, 136, 777; M. M. Hansmann, R. L. Melen, F. Rominger, A. S. K. Hashmi, D. W. Stephan Chem. Commun. 2014, 50, 7243.

Oral presentation - A09

Super-strained inorganic ligands: substrate-dependent reactivity R. Streubel,* J. M. Villalba Franco, A. Espinosa Ferao, V. Nesterov [email protected] Institut für Anorganische Chemie, Rheinischen-Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Str. 1, GER-53121 Bonn Recently, synthesis of complexes I ([M] = M(CO)5; E, E’ = NR) bearing superstrained inorganic P-ligands was achieved using Li/X phosphinidenoid metal complexes and carbodiimides;[1] evidence for related transient species I (E = CR2, E’ = O; E,E’ = O)[2,3] will be provided, too. First studies revealed a multifaceted, substrate-dependent reactivity that is usable under mild conditions: exchange reactions of the carbodiimide unit by other π-units (i),[4] facile ring opening with acidic substrates such as H2O leading to zwitterionic complexes (ii),[1] ring-expansion reactions using monoatomic building blocks such as chalcogen atoms (or others) (iii),[5] or a substrate-responsive FLP-type reactivity (iv), i.e. ring-expansion using isocyanates or carbon dioxide.[4] DFT calculated reaction pathways will be presented.

Figure 1. Reactivity of super-strained rings.

Acknowledgements: We are grateful to the DFG (STR 411/26-3) for financial support. References: [1] J. M. Villalba Franco, Takahiro Sasamori, G. Schnakenburg, A. Espinosa Ferao, R. Streubel, Chem. Commun. 2015,51, 3878-3881. [2] V. Nesterov, G. Schnakenburg, R. Streubel, to be published. [3] C. Schulten, G. von Frantzius, A. Espinosa Ferao, G. Schnakenburg, R. Streubel, Chem. Sci. 2012, 3, 3526-3533. [4] J. M. Villalba Franco, Takahiro Sasamori, G. Schnakenburg, A. Espinosa Ferao, R. Streubel, Chem. Commun. 2015, submitted. [5] J. M. Villalba Franco, G. Schnakenburg, R. Streubel, to be published.

Oral presentation - A10

Hetero deoxy-Breslow intermediates – and more László Nyulászi,* Zsolt Kelemen [email protected] Department of Inorganic and Analytical Chemistry, Budapest University of Technology and Economics Műegyetem rkp 3, H-1111, Budapest, Hungary N-heterocyclic carbenes (NHC) emerged as important stabilizing ligands in main group chemistry.[1] With subvalent compounds X (CH2, SiH2, NH, PH, O, S) NHC and the isomeric abnormal NHCs (aNHC) form stable deoxy-Breslow type mesoionic compounds 1 and 2. These compounds have also possible H-shifted isomers 3 and 4, which are themselves substituted aNHC and NHC, respectively. In a computational analysis we present a comprehensive investigation on the relative stabilites of 1-4, revealing that for the nitrogen and phosphorus compounds the energy of the two Hshifted forms (2 and 4) are close to each other, giving rise for a possible tautomeric equilibrium, which can be fine-tuned by proper substituents. The relative stability of the (substituted) abnormal carbenes (3) with respect to 4 does not depend on the type of substituent. The stability of the mesoionic forms 1 and 2 is related to the electronegativity of the heteroatom in X, the second and third row heteroatoms exerting, however, different stabilization, which is related to the double bond energy. NRT analysis revealed that the contribution of the double bonded resonance structures for 1 and 2 is higher for the second than for the third row elements, which have larger ionic contributions, in agreement with their large pz orbital contribution in the π-type HOMO. NICS aromaticity is in accordance with the weight of the double bonded resonance structures. The electronic structure and the double bond character of the related compounds 1 and 2 with hypervalent heteroatoms X (SiR4, PR3, SR2) will also be discussed.

Acknowledgements: OTKA K 105417 and COST CM1302 is gratefully acknowledged References: [1] (a) M. N. Hopkinson, C. Richter, M. Schedler, F. Glorius Nature 2014, 510, 485. (b) D. Martin, M. Soleilhavoup, G. Bertrand Chem. Sci. 2011, 2, 389.

Oral presentation - A11

Unusual Reactivity of Alkali Metal Oligophosphanediides Anup Kumar Adhikari, Ivana Jevtovikj, Peter Lönnecke, Evamarie Hey-Hawkins* [email protected] Institute of Inorganic Chemistry, Universität Leipzig Johannisallee 29, GER-04103 Leipzig The chemistry of cyclic oligophosphorus compounds has developed impressively over the last few decades. These species can exists as three-, four-, five-, and sixmembered rings and their stability and structures have been extensively investigated.[1] In contrast, the targeted synthesis and properties of linear and cyclic oligophosphanide anions have been studied in detail only recently. Some examples of their reactivity have also been reported, and these studies already indicate a rich and versatile chemistry.[2] Recently, we have obtained a new type of neutral cyclic oligophosphane, namely N(tetramesityltetraphosphacyclopentylidene)cyclohexylamine, by the 1:2 reaction of Na2P4Mes4 (Mes = 2,4,6-Me3C6H2) and cyclohexyl isocyanide. The corresponding copper(I) complex was obtained by reaction with [CuBr(SMe2)]. In contrast, P−P bond cleavage was observed in the reaction of Na2(P4Mes4) with nBuLi leading to a phosphaindazole anion, (P2C9H9)‒ (Figure 1).[3]

Figure 1. Polymeric structure of sodium phosphaindazole anion; chains are oriented parallel to the b axis. H atoms are omitted for clarity.

Acknowledgements: This work was supported by the DAAD (Deutscher Akademischer Austausch Dienst, GSSP scholarship for A.K.A.), the Graduate School BuildMoNa and the EU COST Action CM1302 Smart Inorganic Polymers (SIPs). References: [1] a) M. Baudler, Pure Appl. Chem., 1980, 52, 755; b) M. Baudler, K. Glinka, Chem. Rev., 1993, 93, 1623. [2] a) S. Gómez-Ruiz, E. Hey-Hawkins, Coord. Chem. Rev., 2011, 255, 1360; b) I. Jevtovikj, P. Lönnecke, E. Hey-Hawkins, Chem. Commun., 2013, 49, 7355. [3] I. Jevtovikj, M. B. Sárosi, A. K. Adhikari, P. Lönnecke, E. Hey-Hawkins, Eur. J. Inorg. Chem., 2015, in press.

Oral presentation - A12

Stable Silanetriols – Building Blocks for Rings and Cages Rudolf Pietschnig [email protected] Institute of Chemistry and CINSaT, University of Kassel Heinrich-Plett-Strasse 40, 34132 Kassel, Germany In neutral silanetriols the maximum number of polar silanol groups is attached to the same silicon atom besides an organic substituent. Since the first preparation[1] and structural characterization[2] the main research focus for this type of compounds has been mainly devoted to their synthesis, solid state structures and conversion to metallasiloxanes.[3,4] We are interested to extend the scope of this unusual class of compounds to the liquid state and especially to solutions where aggregation and micelle formation can be observed.[5,6] Besides their surfactant properties silanetriols are also ideal precursors for controlled surface modifications.[7] Moreover, silanetriols can be converted to rings and cages using controlled condensation reactions.[8,9]

References: [1] T. Takiguchi, J. Am. Chem. Soc. 1959, 81, 2359. [2] H. Ishida, J. L. Koenig, K. C. Gardner, J. Chem. Phys. 1982, 77, 5748. [3] P. D. Lickiss, in Chemistry of Organic Silicon Compounds, Vol. 3 (Eds.: Z. Rappoport, Y. Apeloig), Wiley, Chichester, UK, 2001, 695. [4] Murugavel, R.; Voigt, A.; Walawalkar, M. G.; Roesky, H. W. Chem. Rev. 1996, 96, 2205. [5] N. Hurkes, H. Ehmann, M. List, S. Spirk, M. Bussiek, F. Belaj, R. Pietschnig, Chem. Eur. J. 2014, 20, 9330. [6] S. Spirk, S. Salentinig, K. Zangger, F. Belaj, R. Pietschnig, Supramol. Chem. 2011, 23, 801. [7] S. Spirk, H. Ehmann, M. Reischl, R. Kargl, N. Hurkes, M. Wu, J. Novak, R. Resel, R. Pietschnig, V. Ribitsch, Appl. Mat. Interf. 2010, 2, 2956. [8] S. Spirk, M. Nieger, F. Belaj, R. Pietschnig, Dalton Trans. 2009, 163. [9] N. Hurkes, C. Bruhn, F. Belaj, R. Pietschnig, Organometallics 2014, 33, 7299.

Oral presentation - A13

Cyclic Derivatives of Group 14 in Material Science H. Amenitsch, J. Binder, A. Torvisco, M. Wolf, C. Zeppek, F. Uhlig* [email protected] Institute of Inorganic Chemistry, Graz University of Technology Stremayrgasse 9, A-8010 Graz, Austria Cyclic silicon, germanium and/or tin containing derivatives are a well explored field in organometallic chemistry. Over the years our institute has also reported on the syntheses of novel compounds of this type. In extension of this work, we will present here on the synthesis and characterization of such derivatives as well as their applications in material science. We discuss here the synthesis and analytical characterization of a series of novel compounds of type (R2E)n (n = 4-7; R = aryl, H; E = Si, Ge, Sn) displaying in some cases a surprising reaction behavior. Furthermore reactions for the formation of nanoparticles by using such derivatives as precursors are presented together with preliminary results of their use in novel energy storage materials. All compounds are characterized by state-of-the-art analytical methods including scattering techniques and electrochemical characterizations.

Figure 1. Core-shell tin nanoparticles

Acknowledgements: The NAWI Graz-project is gratefully acknowledged for the financial support of this work. Furthermore, we thank ELETTRA Synchrotrone Trieste for their outstanding collaboration.

Oral presentation - A14

Captivating Organotin Anions – Cages, Rings and Chains Roland C. Fischer,* Michaela Flock, Michael S. Hill, David J. Liptrot, Kathrin Schittelkopf, Beate Steller [email protected] Institute for Inorganic Chemistry, Graz University of Technology, Stremayrgasse 9/V, A-8010 Graz, Austria Owing to the high reactivity of the tin-hydrogen bond, aryltinhydrides are versatile building blocks for the formation of oligo- and polystannanes. Therefore, we investigated the reactivity of diphenyltindihydride against alkali metals and alkali metal reagents. In the course of our studies, we developed convenient and high-yield routes towards a surprisingly rich variety of bicyclic, cyclic and acyclic mono-, diand tri-metallated oligostannanes. (Fig. 1). Mechanistic investigations of the Sn-Sn bond formation allowed for the directed synthesis of the title compounds. Trends in their chemical reactivity together with structural and spectroscopic properties will be discussed.

Figure 1. Bicyclic, cyclic and acyclic oligostannides derived from Ph2SnH2.

Acknowledgements: The COST action CM1302 ‘Smart Inorganic Polymers’ is gratefully acknowledged. References: [1] a) P. Riviere, A: Castel, M. Riviere-Baudet, Alkaline and alkaline earth metal-14 compounds in: The Chemistry of organic germanium, tin and lead compounds, Vol. 2 Part 1. (Ed Z. Rappoport), Wiley, Chichester, 2002, p 653ff. b) C. Zeppek, A. Torvisco, R. C. Fischer, F. Uhlig, Can. J. Chem., 2014, 92, 556. c) K. Schittelkopf, R. C. Fischer, S. Meyer, P. Wilfling, F. Uhlig, Appl. Organomet. Chem., 2010, 24, 897. d) T. Schollmeier, U. Englich, R. Fischer, I. Prass, K. Ruhlandt, M. Schürmann, F. Uhlig, Z. Naturforsch. B, 2004, 59b, 1462.

Oral presentation - A15

Transformations of Small Inorganic Molecules by Low-valent Transition Metalate Anions and Transition Metal Radicals Robert Wolf,* Uttam Chakraborty,(a) Stefan Pelties,(a) Niels van Velzen,(b) and Sjoerd Harder(b) [email protected] (a) University of Regensburg, Institute of Inorganic Chemistry, D-93040 Regensburg; (b) Chair of Inorganic and Organometallic Chemistry, University ErlangenNürnberg, Egerlandstraße 1, D-91058 Erlangen This talk will discuss the chemistry of new low-oxidation state cyclopentadienyl iron, cobalt and nickel complexes. The first part will describe the synthesis of Nheterocyclic carbene-stabilized cyclopentadienylnickel(I) radicals.[1] The complexes have a modular structure that allows the modification of their steric and electronic properties. The reactivity of these new nickel(I) radicals with radical traps such as white phosphorus and elemental sulfur will be examined. The second part will discuss the chemistry of new pentarylcyclopentadienyl complexes.[2] These uncommon Cp derivatives are able to stabilize compounds with unusual structures and reactivity patterns as illustrated for example by the synthesis of the first tetraphosphacyclobutadiene iron complex, [CpAr5Fe(cyclo-P4)]- and the dinuclear hexasulfide [(CpAr5Ni)2(µ-S6)] (Figure 1).

Figure 1. Reactivity of new cyclopentadienyl iron and nickel complexes.

Acknowledgements: We thank Moritz Modl and Prof. Manfred Scheer (University of Regensburg) for collaborating on CpBig chemistry. References: [1] S. Pelties, D. Herrmann, B. de Bruin, F. Hartl, R. Wolf, Chem. Commun. 2014, 50, 7014-7016. [2] a) W. Kläui, L. Ramacher, Angew. Chem. Int. Ed. Engl. 1986, 25, 97-98; b) H. Schumann, A. Lentz, R. Weimann, J. Pickardt, Angew. Chem. Int. Ed. Engl. 1994, 33, 1731-1733; c) C. Ruspic, J. R. Moss, M. Schürmann, S. Harder, Angew. Chem. Int. Ed. 2008, 47, 2121-2126.; d) L. D. Field, C. M. Lindall, A. F. Masters, G. K. B. Clentsmith, Coord. Chem. Rev. 2011, 255,1733-1790.

Oral presentation - A16

Pyramidanes: the Covalent Form of an Ionic Compound V. Lee,1* O. Gapurenko,2 Y. Ito,1T. Meguro,1H. Sugasawa,1A. Sekiguchi,1 R. Minyaev,2V. Minkin,2H. Gornitzka,3R. Herber4 [email protected] 1

Department of Chemistry, University of Tsukuba University of Tsukuba, Japan; 2Southern Federal University, Rostov on Don, Russia; 3 Université de Toulouse, France; 4Hebrew University, Israel

Pyramidanes, the square-pyramidal compounds, represent a novel highly challenging class of strained polyhedral clusters featuring an “invertedly” tetrahedral apical atom. Well-studied on theoretical grounds, pyramidane and its derivatives eluded experimental realization until very recently. In this presentation, we report on a series of the first ever prepared group 14 element pyramidanes 1 with the C4/Si4/Ge4 -bases and Ge/Sn/Pb-apexes (Figure).[1] Based on the combined experimental [X-ray crystallography, 13C and 119Sn NMR spectroscopy, Mössbauer spectroscopy, reactivity studies] and computational [frontier MO, NBO/NPA, topological analysis (AIM and ELF)] data, we found a remarkable lone pair character at the apical atom E’. This gives rise to a high degree of ionicity in the E’–E apex-to-base bonds and thus notable contribution of the {[E4]2––[E’]2+} cyclobutadiene dianion–apical atom dication ionic resonance form to the overall composition of the formally neutral pyramidanes.

Figure 1. Pyramidanes 1.

Acknowledgements: This work was supported by the Japanese Society for the Promotion of Science (23655027, 24245007, 24550038, 90143164), Russian Foundation for Basic Research (14-03-92101) and Russian Scientific Schools (NSh-274.2014.3). References: [1] (a) V. Ya. Lee, Y. Ito, A. Sekiguchi, H. Gornitzka, O. A. Gapurenko, V. I. Minkin, R. M. Minyaev, J. Am. Chem. Soc., 2013, 135, 8794; (b) V. Ya. Lee, Y. Ito, O. A. Gapurenko, A. Sekiguchi, V. I. Minkin, R. M. Minyaev, H. Gornitzka, Angew. Chem. Int. Ed., 2015, 54, Early View [DOI: 10.1002/anie.201500731].

Oral presentation - A17

Stable N-Heterocyclic Carbenes with a 1,1’-Ferrocenediyl Backbone and Their Heavier Homologues Ulrich Siemeling*, Christian Färber, Jan Oetzel, Michael Leibold, Clemens Bruhn [email protected] Institute of Chemistry, University of Kassel Heinrich-Plett-Str. 40, GER-34132, Kassel N-Heterocyclic carbenes (NHCs)[1] are extremely valuable as nucleophilic organocatalysts. They are widely applied as ligands in transition-metal catalyzed reactions, where they are known as particularly potent σ-donors. They are commonly viewed as workhorses exhibiting reliable, but undramatic, chemical behavior. We recently demonstrated that a stable ferrocene-based NHC (Fig. 1, left) is able to add ammonia, methyl acrylate, tert-butyl isocyanide, and carbon monoxide under mild conditions.[2] Such small-molecule activation reactions are typical of (alkyl)(amino)carbenes, but were completely unprecedented for diaminocarbenes.[3] In view of the surprising reactivity of this ferrocene-based NHC, which is due to its ambiphilic nature,[4] we surmised that its heavier homologues (Fig. 1, right), too, can be expected to show exceptional chemical behavior. While the synthesis and isolation of corresponding germylenes and stannylenes turned out to be easily possible, we are still hot on the heels of stable or persistent silylenes and plumbylenes. We have been able to obtain a persistent silylenoid, and we have structurally characterized the C-H activation product of a reactive plumbylene.

Figure 1. A stable ferrocene-based NHC (XRD result, left) and its heavier homologues (right).

Acknowledgements: We are grateful to the DFG for generous funding. References: [1] M. N. Hopkinson, C. Richter, M. Schedler, F. Glorius, Nature 2014, 510, 485. [2] U. Siemeling, C. Färber, C. Bruhn, M. Leibold, D. Selent, W. Baumann, M. von Hopffgarten, C. Goedecke, G. Frenking, Chem. Sci. 2010, 1, 697. [3] D. Martin, M. Soleilhavoup, G. Bertrand, Chem. Sci. 2011, 2, 389. [4] C. Goedecke, M. Leibold, U. Siemeling, G. Frenking, J. Am. Chem. Soc. 2011, 133, 3557.

Oral presentation - A18

Sila- and Germacyclopentadienyl Based Radicals C. R. W. Reinhold, B. Urschel, T. Müller* [email protected] Institute of Chemistry Carl von Ossietzky University Oldenburg Carl von Ossietzky Straße 9-11, D-26129 Oldenburg, FRG The remarkable electronic and photophysical properties of group 14 elementcyclopentadienes (tetroles) are well-described and already found applications in OLEDs.[1,2] The results of quantum mechanical calculations predict a stability for the corresponding tetrolyl radicals similar to that of the well-investigated aroxyl based radicals and polyradicals. The addition of unpaired spins to the tetroles could lead to new materials with interesting properties.[3] In this contribution, we will report on our attempts to generate silolyl and germolyl radicals either by reaction of persistent radicals with H-tetroles (Figure, eq. 1) or by reduction of the corresponding halides (Figure, eq. 2)

Figure 1. Synthesis of tetrolyl radicals and ESR spectra of the corresponding germanium(left) and silicon- (right) centered radicals.

Acknowledgements: This work is supported by the CvO University. We thank Drs. Boris Tumanskii and Dmitri Bravo-Zhivotovskii for many valuable discussions. References: [1] J. Dubac, A. Laporterie, G. Manuel, Chem. Rev. 1990,90, 215. [2] S. Yamaguchi, K. Tamao, J. Chem. Soc., Dalton Trans. 1998,3693. [3] T. Nozawa, A. Sekiguchi, M. Ichinohe J. Am. Chem. Soc. 2011, 133, 5773.

Oral presentation - A19

Reactions of tricyclopentasilane and related cyclic silicon compounds with bulky alkyl substituents Takeaki Iwamoto,* Naohiko Akasaka, Shintaro Ishida [email protected] Department of Chemistry, Graduate School of Science, Tohoku University 6-3 Aramakiazaaoba, Aoba-ku, Sendai 980-8578, Japan Polycyclic oligosilanes (molecular silicon clusters) have been extensively studied because they exhibit unique electronic structures due to delocalization of σ(Si–Si) electrons over the silicon frameworks. Recently several molecular silicon clusters bearing three-coordinate silicon vertices with no substituents and/or highly strained four-coordinate silicon vertices in the silicon frameworks (siliconoids[1f]) have been synthesized and their unique structures and reactions are investigated.[1] One of the fascinating reactions is a disproportionation reaction involving expansion or contraction of the silicon frameworks. Scheschkewitz and coworkers have demonstrated thermal disproportionation reactions of an Si6R6 isomer.[1f] Very recently we have synthesized peralkyltricyclo[2.1.0.01,3]pentasilane 1 (Chart 1) and found that it undergoes thermal disproportionation reactions to give new molecular silicon cluster 2.[2] Detailed analysis of the thermal reaction of 1 indicated that tetrasilabicyclo[1.1.0]but-1(2)-ene 3 resulting from elimination of dialkylsilylene unit 4 from 1 was a key intermediate for formation of 2. In the present paper, we wish to report on recent results on thermal reaction of 1 and related molecular silicon clusters.

Figure 1. Compounds 1-4

References: [1] (a) D. Scheschkewitz, Angew. Chem. Int. Ed. 2005, 44, 2954. (b) G. Fischer, V. Huch, P. Mayer, S, K. Vasisht, M. Veith, N. Wiberg, Angew. Chem. Int. Ed. 2005, 44, 7884. (c) D. Nied, R. öppe, W. Klopper, H. Schnöckel, F. Breher, J. Am. Chem. Soc. 2010, 132, 10264. (d) K. Abersfelder, A. J. P. White, H. S. Rzepa, D. Scheschkewitz, Science 2010, 327, 564. (e) K. Abersfelder, A. J. P, White, R. J. F.; Berger, H. S. Rzepa, D. Scheschkewitz, Angew. Chem., Int. Ed. 2011, 50, 7936 (f) K. Abersfelder, A. Russell, H. S. Rzepa, A. J. P. White, P. R. Haycock, D. Scheschkewitz, J. Am. Chem. Soc. 2012, 134, 16008. [2] T. Iwamoto, N. Akasaka, S. Ishida, Nat. Commun. 2014, 5, 5353.

Oral presentation - A20

Synthesis of 1,2-Digermacyclobutene Derivatives and Their Reactions with Ethylene Takahiro Sasamori,* Tomohiro Sugahara, Tomohiro Agou, Koh Sugamata, JingDong Guo, Shigeru Nagase, and Norihiro Tokitoh [email protected] Institute for Chemical Research, Kyoto Univ. Gokasho, Uji, Kyoto 611-0011, JAPAN Triple-bond compounds between heavier group 14 elements, group 14 dimetallynes, have attracted many chemists from the viewpoints of their unique physical and chemical properties.[1] Although these multiple bond compounds are difficult to be isolated due to their inherent extremely high reactivity towards the addition reaction with moisture and/or aerobic oxygen and self-oligomerization, it has been evidenced that such reactive species can be isolated when they are well kinetically stabilized by sterically demanding substituents with keeping their intrinsic nature of reactivity. Nowadays, many examples of the stable group 14 dimetallynes have been reported. Reactions of the stable disilynes with alkenes were reported to give the corresponding 1,2-disilacyclobutene derivatives via formal [2+2] cycloaddition reactions.[2] Here we will report the synthesis and isolation of the stable 1,2-digermacyclobutene by reactions of the stable digermyne, BbtGeGeBbt (Bbt = 2,6-[CH(SiMe3)2]-4[C(SiMe3)3]-C6H2),[3] with alkenes. In addition, the chemical and physical properties of the obtained 1,2-digermacyclobutenes will also be described.

References: [1] R. C. Fischer, P. P. Power, Chem. Rev. 2010, 110, 3877. [2] (a) R. Kinjo, M. Ichinohe, A. Sekiguchi, N. Takagi, M. Sumimoto, S. Nagase, J. Am. Chem. Soc. 2007, 129, 7766. (b) N. Wiberg, S. K. Vasisht, G. Fischer, P. Mayer, Z. Anorg. Allg. Chem. 2004, 630, 1823. [3] Y. Sugiyama, T. Sasamori, Y. Hosoi, Y. Furukawa, N. Takagi, S. Nagase, N. Tokitoh, J. Am. Chem. Soc. 2006, 128, 1023.

Oral presentation - A21

Synthesis, Molecular Structure and Reactivity of Cyclic Sn–P-Lewis Pairs S. Freitag, K. Krebs, J. Schneider, L. Wesemann* [email protected] Institut für Anorganische Chemie, University of Tübingen Auf der Morgenstelle 18, 72076 Tübingen Chemistry of intramolecular stannylene based Lewis pairs is presented.[1] Starting with the terphenyl substituted tin chloride ArSnCl the cyclic molecules 1 and 2 were synthesized in high yield following a straightforward nucleophilic substitution at the tin atom (Equation 1).[2] The substitution products 1 and 2 show an intramolecular Sn–P bond in solution and solid state. The reactivity of these cyclic molecules towards olefins (3), alkynes (4), aldehydes, ketones and azides is discussed (Equation 2). In the case of 1-pentene we found reversible and regioselective addition of the olefin to give the cyclopentane 3. Furthermore in reaction with transition metal fragments of the nickel triad the Lewis pairs 1 and 2 show coordination of tin and phosphorus at the transition metal. In dependency on the coordinating co ligand or temperature the stannylene moiety exhibits a switch from donor (5) to acceptor (6) character (Equation 3).[3]

Figure 1. Equation 1-3 (Ar =C6H3-2,6-Trip2, Trip = C6H2-2,4,6-iPr3, R` = SiMe3, Ph, R = iPr) References: [1] a) S. Freitag, J. Henning, H. Schubert, L. Wesemann, Angew. Chem., Int. Ed. 2013, 52, 5640-5643; b) S. Freitag, K. M. Krebs, J. Henning, J. Hirdler, H. Schubert, L. Wesemann, Organometallics 2013, 32, 6785-6791. [2] B. E. Eichler, L. Pu, M. Stender, P. P. Power, Polyhedron 2001, 20, 551-556. [3] K. M. Krebs, S. Freitag, H. Schubert, B. Gerke, R. Pöttgen, L. Wesemann, Chem.-Eur. J. 2015, in press.

Oral presentation - A22

Synthesis, Structures and Reactions of Antiaromatic Organolead Compounds Stabilized by Lewis Bases Masaichi Saito* (a) Tomoki Akiba,(a) Marisa Nakada,(a) Misumi Kaneko, (a) Shunsuke Furukawa,(a) Mao Minoura,(b) Masahiko Hada(c) [email protected] (a) Department of Chemistry, Graduate School of Science and Engineering, Saitama University, Shimo-okubo, Sakura-ku, Saitama-city, Saitama, 338-8570, JAPAN (b) Department of Chemistry, Graduate School of Science and Engineering, Tokyo Metropolitan University (c) Department of Chemistry, College of Science, Rikkyo University Antiaromaticity, first proposed by Breslow,[1] is used to explain peculiar instability of the cyclic conjugated compounds with 4np electrons. However, antiaromaticity of compounds with heavy group 1 atoms in the π-frameworks remains elusive, even though a few analogues of cyclobutadiene containing heavy group 14 atoms have already been synthesized.[2] We focus on metallacyclopentadienylidene as another possible antiaromatic compound bearing a heavy group 14 atom in the skeleton. In the course of our studies on organolead compounds with unique electronic structures,[3] we report herein the synthesis of a base-stabilized plumbacyclopentadinylidene 1 from 1,4-dilithio-1,3-butadiene 2[4] and its reactivity and behavior in solution.[5]

Figure 1. Synthesis of Base-stabilized Plumbacyclopentadienylidene

References: [1] R. Breslow, Acc. Chem. Res. 1973, 6, 393. [2] (a) C. Cui, M. M. Olmstead, P. P. Power, J. Am. Chem. Soc. 2004, 126, 5062; (b) K. Suzuki, T. Matsuo, D. Hashizume, H. Fueno, K. Tanaka, K. Tamao, Science 2011, 331, 1306; (c) S. Inoue, W. Y. Wang, C. Prasang, M. Asay, E. Irran, M. Driess, J. Am. Chem. Soc. 2011, 133, 2868; (d) Y. –F. Yang, G. –J. Cheng, J. Zhu, X. Zhang, S. Inoue, Y. –D. Wu, Chem. Eur. J. 2012, 18, 7516; (e) H-X. Yeong, H-W. Xi, Y. Li, S. B. Kunnappilly, B. Chen, K-C. Lau, H. Hirao, K. H. Lim, C-W. So, Chem. Eur. J. 2013, 19, 14726. [3] M. Saito, M. Sakaguchi, T. Tajima, K. Ishimura, S. Nagase, M. Hada, Science 2010, 328, 339. [4] M. Saito, M. Nakamura, T. Tajima, M. Yoshioka, Angew. Chem., Int. Ed. 2007, 46, 1504. [5] (a) M. Saito, T. Akiba, M. Kaneko, T. Kawamura, M. Abe, M. Hada, M. Minoura, Chem. Eur. J. 2013, 19, 16946; (b) T. Kawamura, M. Abe, M. Saito, M. Hada, J. Comput. Chem. 2014, 35, 847; (c) M. Saito, M. Nakada, T. Kuwabara and M. Minoura, Chem. Commun. 2015, 51, 4674.

Oral presentation - A23

Chemistry Applying Metalloid Tin Clusters Andreas Schnepf, Claudio Schrenk [email protected] Department of Chemistry, University of Tübingen Auf der Morgenstelle 18, 72076 Tübingen Starting from Sn(I) halides, available via a preparative co condensation technique we could establish a fruitful route to metalloid tin clusters in recent years.[1] These clusters give us a first direct insight into the fascinating area between molecules and the solid state,[2] whereby we could show that novel structural motives are realized in this borderland. Hence zentaurpolyhedral arrangements of 10 tin atoms in such metalloid clusters seem quite favorable, e.g. within the neutral metalloid cluster Sn10[Si(SiMe3)3]6 1.[3] However, the cluster core of 1 is completely shielded by the ligand shell and thus subsequent reactions are difficult as the reactive naked tin atoms are not available. Applying now a Sn(I)Cl solution for the synthesis of metalloid clusters we were able to obtain the open anionic metalloid tin cluster [Sn10[Si(SiMe3)3]4]2- 2[4] in quite high yield. In 2 the tin atoms are now incompletely shielded by the ligand shell so that subsequent reactions seem possible. Hence a first step towards chemistry with metalloid clusters was done and we describe first investigations concerning the physical and chemical properties of 2.

Figure 1. Molecular Structure of [Sn10[Si(SiMe3)3]4]2- 2

References: [1] C. Schrenk, R. Köppe, I. Schellenberg, R. Pöttgen, A. Schnepf, Z. Anorg. Allg. Chem. 2009, 635, 1541-1548. [2] A. Schnepf, Angew. Chem. Int. Ed. 2004 43, 664 – 666, A. Schnepf, Chem. Soc. Rev. 2007, 36, 745-758. [3] C. Schrenk, I. Schellenberg, R. Pöttgen, A. Schnepf, Dalton Trans. 2010, 39, 1872 – 1876. [4] C. Schrenk, A. Kubas, K. Fink, A. Schnepf, Angew. Chem. Int. Ed. 2011 50, 7237 – 7277. C. Schrenk, F. Winter, R. Pöttgen, A. Schnepf, Chemistry, 2015, DOI: 10.1002/chem.201405595.

Oral presentation - A24

Ternary Intermetalloid Clusters: About Unexpected Structures and How to Get There Stefanie Dehnen* [email protected] Fachbereich Chemie and Wissenschaftliches Zentrum für Materialwissenschaften, Philipps-Universität Marburg Hans-Meerwein-Straße, D-35032 Marburg, Germany Heterometallic cluster compounds are currently actively investigated by many research groups, leading from structural studies through functional analyses to the generation of innovative materials.[1] Binary main group element aggregates [E13/14xE14/15y]q– (E13/14/15 = Ga, In, Tl; Ge, Sn, Pb; As, Sb, Bi), hence binary Zintlanions, proved to be useful synthetic tools in reactions with transition metal compounds for assembling ternary intermetalloid clusters [MxE13/14yE14/15z]q–.[2] The latter possess a large variety of different structural motifs and corresponding electronic properties, subject to the nature of the involved elements. Unprecedented, non-classical structures helped to gain deeper insight in the formation of such aggregates (see Figure).[7]

Figure 1. Formation of non-deltahedral intermetalloid clusters from a deltahedral precursor Acknowledgements: This work was supported by Deutsche Forschungsgemeinschaft, Alexander von Humboldt Stiftung and Friedrich Ebert Stiftung References: [1] S. Scharfe, F. Kraus, S. Stegmaier, A. Schier, T. F. Fässler, Angew. Chem. Int. Ed. 2011, 50, 3630. [2] F. Lips, R. Clérac, S. Dehnen, J. Am. Chem. Soc. 2011, 133, 14168. [3] F. ips, M. Hołyńska, R. Clerac, U. inne, I. Schellenberg, R. Pöttgen, F.Weigend, S. Dehnen, J. Am. Chem. Soc. 2012, 134, 1181. [4] R. Ababei, W. Massa, K. Harms, X. Xie, F. Weigend, S. Dehnen, Angew. Chem. Int. Ed. 2013, 52, 13544. [5] B. Weinert, F. Müller, K. Harms, S. Dehnen, Angew. Chem. Int. Ed. 2014, 53, 11979. [6] B. Weinert, A.R. Eulenstein, R. Ababei, S. Dehnen, Angew. Chem. Int. Ed. 2014, 53, 4704. [7] S. Mitzinger, L. Broeckaert, W. Massa, F. Weigend, S. Dehnen, 2015, submitted.

Oral presentation - A25

Base-Stabilized Low Valent Group 14 Element Complexes for the Construction of Unsaturated Systems Cheuk-Wai So [email protected] Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University 21 Nanyang Link, 637371 Singapore The base-stabilized group 14 element(I) dimers can serve as synthons for the preparation of group 14 elements-containing aromatic/delocalized π-conjugated systems. Firstly, the first examples of the 2,6-diiminophenyl-stabilized germanium(I), tin(I) and lead(I) dimers [{2,6-(CH=NAr)2C6H3}E:]2 (E = Ge, Sn, Pb; Ar = 2,6iPr2C6H3) can be reduced by alkali metal to form novel aromatic low valent group 14 analogue of indenyl anions [{2,6-(CH=NAr)2C6H3}E:]- and the radical anion [{2,6(CH=NAr)2C6H3}Ge:]·- (1).[1] Secondly, the reaction of the amidinate-stabilized silicon(I) dimer [PhC(NtBu)2Si:]2 with two equivalents of the amido trichlorosilane [L’SiCl3] (L’ = 2,6-iPr2C6H3NSiMe3) and six equivalents of KC8 afforded the extensive n, π, σ-electron delocalized Si4ring [LSi(µ-SiL’)2SiL] (2).[2] In addition, a germanium atom in the zero oxidation state stabilized by the N-heterocylic silylene 3 will be described.[3]

Figure 1. Group 14 elements-containing unsaturated systems

Acknowledgements: This work was supported by ASTAR SERC PSF Grant References: [1] a) S.-P. Chia, R. Ganguly, Y. Li, C.-W. So, Organometallics 2012, 31, 6415; b) S.-P. Chia, H.-X. Yeong, C.-W. So, Inorg. Chem. 2012, 51, 1002; c) S.-P. Chia, H.-W. Xi, Y. Li, K. H. Lim, C.-W. So, Angew. Chem. Int. Ed. 2013, 52, 6298; d) S.-P. Chia, E. Carter, H.-W. Xi, Y. Li, C.-W. So, Angew. Chem. Int. Ed. 2014, 53, 8455. [2] S.-H. Zhang, H.-W. Xi, K. H. Lim, C.-W. So, Angew. Chem. Int. Ed. 2013, 52, 12346. [3] Y.-L. Shan, W.-L. Yim, C.-W. So, Angew. Chem., Int. Ed. 2014, 53, 13155.

Oral presentation - A26

Anion and Cation Complexation by Di- and Multicentered Tin-Based Lewis Acids Klaus Jurkschat* [email protected] Fakultät für Chemie und Chemische Biologie, TU Dortmund Dortmund, GER-44227 In a revival of our earlier interest in di-and multicentered Lewis acids (types A – D) as hosts for anions [1] first results on compounds of types E and F, and related derivatives are reported. Most remarkably, reaction of the compound HC(SnPh2F)3 with fluoride anion reproducibly gives, under partial Sn-C bond cleavage, the unprecedented nona-nuclear tin cluster G.

References: [1] A. S. Wendji, M. Lutter, C. Dietz, V. Jouikov, K. Jurkschat Organometallics 2013, 32, 5720 (and references cited herein).

Oral presentation - A27

New isolated polyborate anions templated by cationic transitionmetal complexes Michael A. Beckett*,(a) Mohammed A. Altahan,(a) and Peter N. Horton(b) [email protected] (a) School of Chemistry, Bangor University, Bangor, Gwynedd, LL57 2UW, UK (b) School of Chemistry, Southampton University, Southampton, SO17 1BG, UK Polyborate anions are conveniently classified as either ‘condensed’ (2D or 3D polymeric chains, sheets or networks) or ‘isolated’ (discrete anionic moieties). Isolated polyborate anions are readily synthesised by the addition of B(OH)3 to a basic aqueous solution containing templating cations, or by solvothermic methods. Templated products arise since B(OH)3in basic aqueous solution exists as a dynamic combinatorial library of polyborate anions. In general, pentaborate(1-) salts (containing the [B5O6(OH)4]- anion) are formed because these salts have a strong Hbonded anionic lattice, which is sufficiently flexible to accommodate many medium sized cations.[1] Salts containing polyborate anions other than pentaborate(1-) are relatively rare. We are interested in the synthesis of structurally novel polyborate anions and have adopted a strategy of templating such species by the use of sterically demanding and/or highly charged cations. Herein, we report the synthesis of several salts containing isolated polyborate anions partnered with transition metal cations and describe the synthesis and structures of novel heptaborate(3-) and octaborate(2-)[2] anions. These anions contain numerous fused B-O rings and cages.

References: [1] (a) M.A. Beckett, S.J. Coles, R.A. Davies, P.N. Horton and C.L. Jones, Dalton Trans., 2015, 44, in press. (Published online 10.3.15) DOI: 10.1039/c5dt00248f. (b) M.A. Beckett, P.N. Horton, M.B. Hursthouse, D.A. Knox, and J.L. Timmis, Dalton Trans, 2010, 39, 3944-3951. [2] M.A. Altahan, M.A. Beckett, S.J. Coles and P.N. Horton, Inorg. Chem., 2015, 54, 412-414.

Oral presentation - B01

Reactivities of a Barrelene-type Dialumane as an Equivalent of an Al=Al Doubly-bonded Species Tomohiro Agou, Koichi Nagata, Takahiro Sasamori, and Norihiro Tokitoh* [email protected] Institute for Chemical Research, Kyoto University Gokasho, Uji, Kyoto 611-0011, Japan Construction of novel element-element bonding has been one of the most important topics in chemistry. However, multiply-bonded compounds involving heavier group 13 elements have remained underdeveloped.[1] Especially, a dialumene (R–Al=Al–R) has never been isolated as a stable compound under ambient conditions. Generation of a 1,2-diaryldialumene was suggested from the isolation of the corresponding [2+4]cycloadduct of the dialu-mene with toluene.[2] In the course of our synthetic studies on dialumenes, we have found that a dialumane (Al–Al singly-bonded species) bearing barrelene-like scaffold ex-hibits reactivities as a synthetic equivalent of the corresponding dialumene.[3-5] The C6H6 moiety of barrelene-type dialumane 1 is readily exchanged with naphtha-lene and bis(trimethylsilyl)acetylene at room temperature, affording the corresponding cyclic dialumanes 2 and 3 (Scheme 1). Formation of dialumanes 2 and 3 are most likely interpreted in terms of the intermediacy of dialumene 4 via thermal retro-cycloaddition of barrelene-type dialumane 1. Reactions of dialumane 1 with other unsaturated compounds as well as transition metal complexes will also be described.

Scheme 1

References: [1] R. C. Fischer, P. P. Power, Chem. Rev. 2010, 110, 3877. [2] R. J. Wright, A. D. Phillips, P. P. Power, J. Am. Chem. Soc. 2003, 125, 10784. [3] T. Agou, K. Nagata, N. Tokitoh, Angew. Chem. Int. Ed. 2013, 52, 10818. [4] K. Nagata, T. Agou, N. Tokitoh, Angew. Chem. Int. Ed. 2014, 53, 3881. [5] T. Agou, K. Nagata, T. Sasamori, N. Tokitoh, Chem. Asian J. 2014, 9, 3099.

Oral presentation - B02

Donor-acceptor complexes of inorganic analogs of benzene Alexey Y. Timoshkin [email protected] Department of Inorganic Chemistry, Institute of Chemistry, St. Petersburg State University Universitetskii pr. 26, 198504 St. Petersburg, Russia Results of experimental and theoretical studies of inorganic benzene analogs: borazine, substituted borazines, polyborazines, alumazene and their donor-acceptor complexes will be presented. Structural and energetic aspects of complex formation and thermal stability of heterocycles and their complexes will be discussed. It is experimentally shown, that solution of B,B’,B”-tribromborazine in deuterobenzene is stable for 14 months, but undergoes fast (within minutes) H/D exchange in presence of Lewis acid AlBr3. Proposed electrophilic substitution mechanism for the exchange is supported by computational studies. In contrast, unsubstituted borazine does not undergo H/D exchange in presence of AlBr3. Hydrogenation reactions of heterocycles will be also discussed. Quantum chemical computations at B3LYP/TZVP level of theory indicate that upon complexation with AlCl3 as a model Lewis acid, both endothermicity and activation energies of hydrogenation processes of borazine (Figure) and polyborazines are significantly reduced. The use of Lewis acids as catalysts in the processes of regeneration of spent hydrogen fuel is recommended.

Figure 1. Energy profile of the hydrogenation process of borazine (red) and its complex with AlCl3 (blue). B3LYP/TZVP level of theory.

Acknowledgements: Financial support from St. Petersburg State University (grant 12.38.255.2014) is acknowledged. References: Lisovenko A.S., Timoshkin A.Y., Inorg. Chem. 2010, 49, 10357–10369. Timoshkin A.Y., Kazakov I.V., Lisovenko A.S., Bodensteiner M., Scheer M., Inorg. Chem. 2011, 50, 9039–9044. Lisovenko A.S., Timoshkin, A.Y., Russ. J. Gen. Chem. 2011, 81, 831–839. Kazakov I.V., Timoshkin, A.Y., Russ. J. Inorg. Chem. 2012, 57, 557–563. Lisovenko A.S., Timoshkin, A.Y., Russ. Chem. Bull. 2012, 61, 897-905.

Oral presentation - B03

Multiply Boron-Nitrogen Doped Hexi-peri-hexabenzocoronene Holger F. Bettinger [email protected] Institut für Organische Chemie, Universität Tübingen Auf der Morgenstelle 18, 72076 Tübingen, Germany BN substitution is an attractive means of changing electronic properties of polycyclic aromatic hydrocarbons (PAH) without changing the molecular and crystal structure. Hexa-peri-hexabenzocoronene (HBC), a representative nanographene molecule,1 is related to its B3N3 derivative, BN-HBC, by substitution of the central aromatic benzene ring by an isoelectronic borazine (“inorganic benzene”) ring. Here we show how BN-HBC can be synthesized and isolated.2 We discuss the usefulness of the partially hydrogenated derivatives (1 and 2) as possible precursors to BN-HBC.

References: 1. a) L. Chen, Y. Hernandez, X. Feng, K. Müllen Angew. Chem. Int. Ed. 2012, 51, 7640; b) H. Seyler, B. Purushothaman, D.J. Jones, A. B. Holmes, W. W. H. Wong Pure Appl. Chem. 2012, 84, 1047. 2. M. Krieg, F. Reicherter, P. Haiss, M. Ströbele, K. Eichele, M.-J. Treanor, R. Schaub, H. F. Bettinger Angew. Chem. Int. Ed. 2015, accepted for publication; (DOI: 10.1002/anie.201412165).

Oral presentation - B04

Main group metal complexes containing hybrid amino/guanidinate (1- or 2-) ligands Jana Nevoralova, Emilie Riemlova, Zdenka Ruzickova, Tomas Chlupaty, Ales Ruzicka* [email protected] Department of General and Inorganic Chemistry Faculty of Chemical Technology, University of Pardubice, Studentska 573, CZ-532 10, Pardubice, Czech Republic Stabilization of unusual[1], generally lower, oxidation states of metals in its complexes containing amidinate/guanidinate ligands opened new areas in various catalyzed organic chemistry transformations[1-3] Similarly applications of these complexes as precursors for preparation of new materials is known.[4] The essential step in synthesis of metal amidinates/guanidinates is the preparation of lithium amidinate/guanidinate or amidine/guanidine precursors, which in contrary to the target compounds are only rarely described in the literature.[5] Synthesis and structure of various kinds hybrid amidinate/guanidinate lithium, dilithium and group 14 complexes will be presented along with the reactivity of these compounds with different metal halides and amides.

Figure 1. Hybrid amino-guanidinato complex

Acknowledgements: The financial support of the Czech Science Foundation (Project no. P207/12/0223) is gratefully acknowledged. References: [1] for example: (a) C. Jones, Coord. Chem. Rev., 2010, 254, 1273; (b) S.S. Sen, S. Khan, S. Nagendran, H.W. Roesky, Acc. Chem. Res., 2012, 45, 578; (c) S. Inoue, J. D. Epping, E. Irran, M. Driess, J. Am. Chem. Soc., 2011, 133, 1 (d) T. Chlupatý, Z. Padělková, A. yčka, J. Brus, A Růžička, Dalton Trans., 2012, 41, 5010. [2] F. T. Edelmann, Chem. Soc. Rev., 2009, 38, 2253; (b) S. Collins, Coord. Chem. Rev., 2011, 255, 118. [3] for example see: (a) Z.-T. Yu, Y.-J Yuan, J.-G. Cai, Z.-G. Zou, Chem. Eur. J., 2013, 19, 1303; (b) J. Kratsch, M. Kuzdrowska, M. Schmid, N. Kazeminejad, C. Kaub, P. Oña-Burgos, S.M. Guillaume, , P.W. Roesky, Organometallics, 2013, 32, 1230. [4] for example: M. Krasnopolski, C. G. Hrib, R.W. Seidel, M. Winter, H.-W. Becker, D. Rogalla, R.A. Fischer, F.T. Edelmann, A. Devi, Inorg. Chem., 2013, 52, 286. [5] T. Chlupaty, R. Olejnik, A. Ruzicka, In: F.L. Tabarés, Ed., Lithium: Technology, Performance and Safety, Chapter 4, Nova Science Publishers, Inc., Hauppauge NY, 2013.

Oral presentation - B05

Chalcogen Macrocycles Incorporating P2N2 Rings and Coinage Metals T. Chivers* (a), R. Thirumoorthi (a), A Nordheider (b), K. Hüll (b), K. S. Athukorala Arachchige (b), A.M.Z. Slawin (b) and JD Woollins (b) [email protected] a) Department of Chemistry, University of Calgary, Calgary, AB, Canada T2N 1N4; b) Department of Chemistry, University of St Andrews, St Andrews, University of Calgary, Calgary, AB, Canada T2N 1N4 Cyclo-P2N2-supported chalcogen macrocycles 1S and 1Se are formed upon twoelectron oxidation of the dianions [E(NtBu)P(µ-NtBu)2P(NtBu)E]2- (E = S, Se) with iodine.1 With a view to incorporating coinage metals into these macrocycles, the metathetical reactions of these dianions with M(I) reagents (M = Ag, Au) were found to produce the trimeric and tetrameric macrocycles 2 and 3, embodying the monoprotonated ligand [Se(NtBu)P(µ-NtBu)2P(HNtBu)Se]- and the intriguing ladder complex 4, which features both monoanionic and dianionic ligands (E = S).2 The formation and structures of 2-4 will be discussed.

References: [1] A. Nordheider, T. Chivers, R. Thirumorthi, I. Vargas-Baca, J. D. Woollins, Chem. Commun. 2012, 48, 6346. [2] A. Nordheider, K. Hüll, K. S. Athukorala Arachchige, A. M. Z. Slawin, J. D. Woollins, R. Thirumoorthi, T. Chivers, Dalton Trans. 2015, 44, 5338.

Oral presentation - B06

Synthesis and Properties of Hypervalent Sulfur Radicals Yohsuke Yamamoto1,* Yasuyuki Imada1, Kukita Tomomi1, Nakano Hideyuki2, Furukawa Ko3, Kishi Ryohei4, Nakano Masayoshi4, Maruyama Hitoshi5, Nakamoto Masaaki5, Sekiguchi Akira5 [email protected] Department of Chemistry, Graduate School of Science, Hiroshima University 1-3-1 Kagamiyama, Higashi-Hiroshima 739-8526, Japan Hypervalent sulfur radicals (sulfuranyl radicals) have nine formal valence electrons in the sulfur atom, and are considered to be intermediates in bimolecular homolytic substitution (SH2) reactions. Although several sulfuranyl radicals have been observed by ESR or UV-vis spectroscopies, they are elusive species and have not been structurally characterized by X-ray analysis. In 1986, Martin et al. reported thermally stable sulfuranyl radical 1 stabilized by a tridentate ligand.[1] Although the sulfuranyl radical was reported to be persistent in solution, it existed in equilibrium with the dimers, and had not been isolated and structurally characterized by X-ray analysis. We envisioned that if the CF3 groups can be replaced by sterically hindered C2F5 groups, dimerization can be inhibited due to the steric hindrance and a sulfuranyl radical can be isolated as a stable monomer, thereby allowing structural characterization. Then, we prepared a new tridentate ligand precursor with C2F5 groups and sulfuranyl radical 2 as a monomer. X-ray crystallography, ESR spectroscopy, and DFT calculation reveal the three- coordinated hypervalent structure of 2. The corresponding hypervalent selenium radical is also isolated and characterized. Properties and application of 2 will be discussed.

References: [1] Perkins, C. W.; Clarkson, R. B.; Martin, J. C. J. Am. Chem. Soc.1986, 108, 3206-3210.

Oral presentation - B07

Synthesis and Characterization of Sulfur-Nitrogen π-Heterocyclic Radical-Anion Salts with Sandwich Organometallic Cations Nikolay A. Semenov, Nikolay A. Pushkarevsky, Lidia S. Konstantinova, Sergey N. Konchenko, Oleg A. Rakitin, Rüdiger Mews, J. Derek Woollins, Andrey V. Zibarev* [email protected] Institute of Organic Chemistry, Russian Academy of Sciences 630090 Novosibirsk, Russia Various new syntheses of inorganic ring systems such as [1,2,5]thiadiazolo[3,4c][1,2,5]thiadiazole (1), its Se congeners and related sulfur/selenium-nitrogen πheterocycles including (aza) benzo-fused ones were performed. Interaction of S derivatives with sandwich organometallics MAr2(M = Cr, Mo) and MCp2(M = Co, Cr) gave sulfur-nitrogen π-heterocyclic radical-anion (RA, S = 1/2) salts with corresponding cations [MAr2]+ and [MCp2]+. The cations were diamagnetic ([CoCp2]+, S = 0) or paramagnetic ([CrCp*2]+, S = 3/2; [CrTol2]+, S = 1/2; and [MoMes2]+, S = 1/2) providing homospin or heterospin salts, respectively. The representative examples are given below. Studying Se congeners is in progress. All salts synthesized were characterized by single-crystal X-ray diffraction (XRD) in combination with solid-state and solution EPR. Their magnetic properties were studied by SQUID magnetometry in temperature range 2-300 K in combination with quantum chemical calculations. The salts revealed complex magnetic structures dominated by antiferromagnetic exchange interactions. At the same time, the presence of weak ferromagnetic interactions in the heterospin salts was also recognized.

Figure 1. Synthesis and XRD structures of the title salts.

Acknowledgements: The authors are grateful to the Leverhulme Trust (IN 2012-094) and Russian Foundation for Basic Research (13-03-00072) for financial support. References: Lonchakov, A. V.; Rakitin, O. A.; Gritsan, N. P.; Zibarev, A. V. Molecules 2013, 18, 9850–9900 (and references therein).

Oral presentation - B08

The Supramolecular Chemistry of Iso-Tellurazole N-Oxides Peter C. Ho, Patrick Szydlowski, Jocelyn Sinclair, Phillip J. W. Elder, Joachim Kübel, 
Chris Gendy, Lucia M. Lee, Ignacio Vargas-Baca* [email protected] Department of Chemistry and Chemical Biology, McMaster University 1280 Main Street West, Hamilton, Ontario, Canada L8S 4M1 Molecules that contain the heaviest chalcogens (Se, Te) often produce crystals which feature supramolecular association.[1] For example, an iso-selenazole N-oxide forms a centrosymmetric dimer through a pair of Se…O contacts that are shorter than the sum of van der Waals radii.[2] In contrast, a tellurium analogue assembles an intriguing annular tetramer.[3] Our recent investigations of these systems have revealed a variety of new supramolecular aggregates built from iso-tellurazole N-oxides that include hexameric rings and polymers (Figure 1). VT NMR spectroscopy demonstrated that the tetra- and hexamers are persistent in solution and exist in equilibrium. These selfassembled structures behave as actual macrocyles that are able to form coordination complexes with transition metal ions and act as fullerene receptors.

Figure 1. Supramolecular species derived from an iso-tellurazole N-oxide. Acknowledgements: The support of the NSERC Canada is gratefully acknowledged. Part of this work was made possible by the facilities of the Shared Hierarchical Academic Research Computing Network (SHARCNET: www.sharcnet.ca) and Compute/Calcul Canada. References: [1] A. F. Cozzolino, P. J. W. Elder, I. Vargas-Baca, Coord. Chem. Rev. 2011, 255, 1426–1438. [2] K. Shimada, A. Moro-oka, A. Maruyama, H. Fujisawa, T. Saito, R. Kawamura, H. Kogawa, M. Sakuraba, Y. Takata, S. Aoyagi, Y. Takikawa, C. Kabuto, Bull. Chem. Soc. Jpn. 2007, 80, 567‑577. [3] J. Kübel, P. J. W. Elder, H. A. Jenkins and I. Vargas-Baca, Dalton Trans. 2010, 39, 11126-11128.

Oral presentation - B09

Mixed d-/f-Metal Polypnictide Complexes Sergey N. Konchenko*, Manfred Scheer, Peter Roesky [email protected] Nikolaev Institute of Inorganic Chemistry SB RAS Prosp. Lavrentieva 3, RF-630090, Novosibirsk The presentation is devoted to collation of recent advances in the field of polypnictide molecular f-metal and mixed d-/f-metal complexes. It is based on summarizing of results of the long-term collaboration between research groups of the authors, and focused on the study of reactivity of Ln(II) compounds towards a variety of polypnictide transition metal complexes.[1] The chemistry can be basically described as one- or two-electron reduction of polypnictide transition metal complexes causing different types of the polypnictide unit transformation inside the coordination sphere of metals, and formation of the mixed d-/f-metal complexes. Some examples of which are shown below (Fig. 1).

Figure 1. Reactions of Cp*2Sm(THF)2 with (i) Cp*FeP5 and (ii) [Cp‴CoP2]2. Alkyl substituents are omitted for clarity.

Acknowledgements: This work was supported by the Deutsche Forschungsgemeinschaft (DFG), the Russian Foundation for Basic Research (RFBR), the Russian Ministry of Education and Science, and the Landesstiftung Baden-Württemberg GmbH. References: [1] (a) T. Li, N. Arleth, M.T. Gamer, R. Koeppe, T. Augenstein, F. Dielmann, M. Scheer, S.N. Konchenko, P.W. Roesky, Inorg. Chem., 2013, 52, 14231; (b) T. Li, M.T. Gamer, M. Scheer, S.N. Konchenko, P.W. Roesky, Chem. Commun., 2013, 49, 2183; (c) T. Li, J. Wiecko, N.A. Pushkarevsky, M.T. Gamer, R. Koeppe, M. Scheer, S.N. Konchenko, P.W. Roesky, Angew. Chem., Int. Ed. Engl., 2011, 50, 9491; (d) S.N. Konchenko, N.A. Pushkarevsky, M.T. Gamer, R. Koeppe, H. Schnoeckel, P. Roesky, J. Am. Chem. Soc., 2009, 131, 5740.

Oral presentation - B10

Phosphorus, Arsenic and Antimony Ligands in Lanthanide Molecular Nanomagnets Thomas Pugh and Richard A. Layfield* [email protected] School of Chemistry The University of Manchester, Oxford Road, Manchester, M13 9PL, U.K. Rare earth metal compounds containing soft heteroatom donor ligands have attracted considerable interest in recent years. The combination of M3+ cations with heavy pblock donor atoms results in a so-called hard-soft "mismatch"[1] that can lead to unusual bonding properties and to distinct reactivity. Within this context, rare earth complexes of anionic phosphorus donor ligands have been extensively studied. Some analogous chemistry with anionic arsenic ligands is known, but such compounds are still very rare. The use of P- and As-donor ligands in the design of lanthanide singlemolecule magnets (SMMs) is, however, entirely unknown.[2,3] In this lecture, the dynamic magnetic properties of a series of dysprosium ring systems with phosphide, phosphinidene, arsenide and arsinidene ligands (Figure 1) will be described.[4-6] The experimental studies are complemented by ab initio calculations, which have enabled us to construct a model for the magnetic anisotropy and magnetization relaxation mechanisms in our SMMs. The theoretical model also provides insight into how SMMs with larger anisotropy barriers may be designed, and selected new systems with antimony-based ligands will also be presented.[7]

Acknowledgements: Financial support from the European Research Council, the Engineering and Physical Sciences Research Council, EU Marie Curie Actions, and the Royal Society is gratefully acknowledged. References: [1] T. Li, S. Kaercher, P. W. Roesky, Chem. Soc. Rev. 2014, 43, 42. [2] D. N. Woodruff, R. E. P. Winpenny, R. A. Layfield, Chem. Rev. 2013, 113, 5110. [3] R. A. Layfield, Organometallics 2014, 33, 1084. [4] T. Pugh, A. Kerridge, R. A. Layfield, Angew. Chem. Int. Ed. 2014, 54, 4255. [5] T. Pugh. L. Ungur, F. Tuna, E. J. L. McInnes, D. Collison, L. F. Chibotaru, R. A. Layfield Nat. Commun. 2015, accepted. [6] T. Pugh, N. F. Chilton, R. A. Layfield, manuscript submitted. [7] Unpublished work.

Oral presentation - B11

QUEST FOR MONOMERIC STIBINIDENES AND BISMUTHINIDENES AS NEW LIGANDS FOR TRANSITION METALS Libor Dostál,* Iva Vránová [email protected] Department of General and Inorganic Chemistry, University of Pardubice Studentká 573, Czech Republic-53210, Pardubice Monomeric stibinidenes and bismuthinedes remained elusive species for a long time. We have succeeded in the isolation of the first examples using of an effective coordination of N,C,N pincer type ligands.1 Recently, analogous stibinidenes have been prepared by Bertrand2 and Hudnall3 using stabilization by carbene ligands. The present studies in our labs is focused on the influence of the structure of particular C,N-chelating ligand on the structure of antimony(I) and bismuth(I) compounds with particular emphasis on the preparation of stibinidenes and bismuthinedes (Figure 1). As both stibinidenes and bismuthinedes formally contain two lone pairs of electrons on the central atom, the preliminary results of their coordination behavior towards transition metal fragments will be discussed.

Figure 1. Structure of studied compounds

Acknowledgements: The authors thank the Grant Agency of the Czech Republic project. no. P207/1506609S. References: [1] Šimon, P. De Proft, F. Jambor, R. Růžička, A. Dostál, . Angew. Chem. Int. Ed. 2010, 49, 5468. [2] Kretschmer, R.; Ruiz, D.A.; Moore, C.E.; Rheingold, A.L.; Bertrand, G. Angew. Chem. Int. Ed. 2014, 53, 8176. [3] Dorsey, C.L.; Mushinski, R.M.; Hudnall, T.W. Chem. Eur. J. 2014, 20, 8914.

Oral presentation - B12

Iron-Catalyzed Routes to Phosphorous-Containing Rings Rory Waterman [email protected] Department of Chemistry, University of Vermont Burlington, VT 05401, USA Transition-metal catalysts can readily convert primary phosphines to cyclo-phosphine products. In contrast, simple iron compound such as CpFeMe(CO)2have demonstrated the ability to reliably convert dicyclohexylphosphine (CyPH2) to P5Cy5in low but reliable conversion where the major product is the expected diphosphine, (Cy2P)2. This observation suggested the extrusion of a phosphinidene fragment that might be trapped with organic substrates. Indeed, primary aryl and alkyl phosphines can be converted to phospholes with alkynes or dienes in the presence of an iron catalyst (eq). Mechanistic study and further synthetic efforts will be presented.

Acknowledgements: This work was supported by the U.S. National Science Foundation. RW acknowledges fellowship support from the Alexander von Humboldt Foundation.

Oral presentation - B13

One, two, three Halogens on the Ring - on the Formation Mechanism of N-Heterocyclic Haloboranes and Halophosphanes Dirk Hermannsdörfer, Manuel Kaaz, Oliver Puntigam, Johannes Bender, Martin Nieger, Dietrich Gudat* [email protected] Institut für Anorganische Chemie, University of Stuttgart Pfaffenwaldring 55, GER-70550 Stuttgart N-heterocyclic haloboranes (NHB, I) and halophosphanes (NHP, II) are important precursors for NHC analogues and may also serve as key intermediates in syntheses of further heterocycles. Their preparation from diazadienes is usually accomplished in two-steps via reduction of the diazadiene by a metal and subsequent ring closing metathesis with a suitable electrophile. In addition, also several reports on one-step syntheses of NHPs[1] and NHBs[2] via (oxidative) cycloadditions are known. Depending on starting materials and reaction conditions, these reactions yield either mono-halogenated (I, II) or dihalogenated heterocycles (III, IV). Here, we report on experimental and computational studies of the reaction mechanism of the cycloaddition processes. Our results provide a systematic understanding of the pathways leading to mono- and dihalogenated heterocycles, and it will be shown how the reaction can be driven into either direction. Furthermore, syntheses of trihalogenosubstituted NHBs and NHP-NHB "adducts" V will be presented.

Figure 1. Molecular structures of NHBs and NHPs (X = Cl, Br, I, R = alkyl, aryl) and NHPNHB "adducts"

References: [1] (a) A. M. Kibardin, I. A. Litvinov, V. A. Naumov, T. Struchkov, Y. Mikhailov, A. N. Pudovik, Dokl. Akad. Nauk. SSSR 1988, 298, 369; (b) M. Kibardin, A. N. Pudovik, Russ. J. Gen. Chem. 1993, 63, 1687; (c) G. Reeske, A. H. Cowley, Inorg. Chem. 2007, 46, 1426; (d) J.W. Dube, G.J. Farrar, E.L. Norton, K. L. S. Szekely, B. F. T. Cooper, C. L. B. Macdonald, Organometallics 2009, 28, 4377. [2] (a) L. Weber, J. Förster, H.-G. Stammler, B. Neumann, Eur. J. Inorg. Chem. 2006, 5048; (b) A. Hinchliffe, F. S. Mair, E. J. L. McInnes, R. G. Pritchard, J. E. Warren, Dalton Trans. 2008, 222. [3] M. Kaaz, J. Bender, D. Förster, W. Frey, M. Nieger, D. Gudat, Dalton Trans. 2014, 43, 680.

Oral presentation - B14

Peri-Interactions within (Ace)Naphthyl Compounds Reloaded Jens Beckmann [email protected] Institut für Anorganische Chemie, Universität Bremen Leobener Str. GER-28359 Bremen The close proximity of peri-substituents in 1,8- and 5,6-positions of naphthalene and acenaphthene gives frequently rise to unique bond situations and codependent reactivity. We are interested in ′through-space′ peri-interactions of diphenylphosphino(ace)naphthyl compounds that can be either repulsive due to steric congestion or attractive due to weak or strong bonding. The potential of selected compounds as ligands for coinage metal salts will be also elaborated.[1-6]

References: [1] J. Beckmann, E. Hupf, E. Lork, S. Mebs, Inorg. Chem. 2013, 52, 11881-11888. [2] E. Hupf, E. Lork, S. Mebs, J. Beckmann, Organometallics 2014, 33, 2409-2423. [3] E. Hupf, E. ork, S. Mebs, . Chęcińska, J. Beckmann, Organometallics 2014, 33, 7247-7259. [4] E. Hupf, E. Lork, S. Mebs,J. Beckmann, Inorg. Chem. 2015, 54, 1847-1859. [ ] A. Nordheider, E. Hupf, B. A. Chalmers, F. R. night, M. Bühl, S. Mebs, . Chęcińska, E. ork, P. Sanz Camacho,S. E. Ashbrook, K. S. Athukorala Arachchige, D. B. Cordes, A. M. Z. Slawin, J. Beckmann, J. D. Woollins, Inorg. Chem. 2015, 54, 2435-2446. [6] J. Brünig, E. Hupf, E. Lork, S. Mebs J. Beckmann, Dalton Trans. 2015, DOI:10.1039/C5DT00588.

Oral presentation - B15

Synthesis and reactivity of phosphinidene boranes Amy N. Price, Michael J. Cowley* [email protected] School of Chemistry, University of Edinburgh Joseph Black Building, West Mains Road, Edinburgh, EH9 3FJ, United Kingdom Phosphinidene boranes, RP=BR, are the heavier homologues of the widely studied imino-boranes, RN=BR. In contrast to the imino-boranes, few examples are known and those that do exist are generally stabilized by coordination of Lewis acids or bases to the phosphorus or boron centres respectively.[1–3] Nevertheless, the reactivity of the as-yet-unknown uncoordinated phosphinidene-boranes, especially given recent progress in the chemistry of the isoelectronic group 14 alkyne analogues, is of high interest. We have recently embarked upon a project designed to prepare the first acid/base-free phosphindene boranes, and here report some preliminary results, including a new high-yielding route to base-stabilised phosphinidene boranes. For example, treatment of the functional phosphino-borane 1 with a range of Lewis bases (e.g. DMAP) results in the formation of base-stabilized phosphinidene boranes such as 2, whilst reactions with larger NHCs lead to desilylation to form 3. We will present details of the synthesis, structure and reactivity of these compounds and related species.

Figure 1. Reactivity of the functional phosphinoborane 1.

Acknowledgements: We gratefully acknowledge the University of Edinburgh and the European commission (Marie Curie CIG to MC) for funding. References: [1] G. Linti, H. Nöth, K. Polborn, R. T. Paine, Angew. Chem. Int. Ed. Engl. 1990, 29, 682–684. [2] E. Rivard, W. A. Merrill, J. C. Fettinger, P. P. Power, Chem. Commun. 2006, 3800–3802. [3] E. Rivard, W. A. Merrill, J. C. Fettinger, R. Wolf, G. H. Spikes, P. P. Power, Inorg. Chem. 2007, 46, 2971–2978.

Oral presentation - B16

Unconventional Ring Sizes with Noninnocent Ligand Components Wolfgang Kaim [email protected] Institut für Anorganische Chemie, Universität Stuttgart Pfaffenwaldring 55, D-70550 Stuttgart, Germany The vast majority of cyclic molecular and coordination compounds with redox-active, i.e. noninnocently behaving ligands involves five-membered (chelate) rings. orthoQuinone, dithiolene and α-diimine complexes are among the best known examples.1 (Formula 1) Only recently have six-membered such rings with a variable number of heteroatoms been reported,2-4 including those with “hidden noninnocence”.2 (Formula 2) The requirement for such unusual arrangements and new examples5 for fourmembered ring species will be presented and their noninnocence will be discussed. (Formula 3)

References: 1 W. Kaim, Inorg. Chem. 2011, 50, 9737-9914. 2 M. M. Khusniyarov, E. Bill, T. Weyhermüller, E. Bothe, K. Wieghardt, Angew. Chem. 2011, 123, 1690-1693; Angew. Chem. Int. Ed. 2011, 50, 1652-1655. 3 H. Agarwala, T. M. Scherer, S. M. Mobin, W. Kaim, G. K. Lahiri, Dalton Trans. 2014, 43, 39393948. 4 M.-C. Chang, T. Dann, D. P. Day, M. Lutz, G. G. Wildgoose, E. Otten, Angew. Chem. 2014, 126, 4202-4206; Angew. Chem. Int. Ed. 2014, 53, 4118-4122. 5 F. Ehret, M. Bubrin, S. Zalis, W. Kaim, Angew. Chem. 2013, 125, 4771-4773; Angew. Chem. Int. Ed. 2013, 52, 4673-4675. 6 F. Ehret, M. Bubrin, S. Zális, W. Kaim, Z. Allg. Anorg. Chem. 2014, 640, 2781-2787.

Oral presentation - B17

The sodium 3,4,5-triaryl-1,2-diphosphacyclopentadienides derivatives: synthesis and coordination properties Ilya A. Bezkishko(a)*, Lilia R. Kochetkova(a), Vasily A. Miluykov(a), Olga N. Kataeva(a), Oleg G. Sinyashin (b) [email protected] (a) A.E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center, Russian Academy of Sciences; Arbuzov str. 8, 420088, Russia, Kazan (b) Leipzig University, Institute of Inorganic Chemistry The 1,2-diphosphacyclopentadienide anion, an isolobal analogue of the Cp- and pyrazolate anion, has an significant interest as ligand in coordination chemistry due to the possibility of realizing various coordination modes with metal atoms[1]. We have found a new convenient synthesis of sodium 3,4,5-triaryl-1,2-diphosphacyclopentadienide and studied their coordination properties. The coordination mode of 1,2-diphosphacyclopenatdienide to metal in obtained complexes determine their magnetic properties.

Acknowledgements: This work was supported by the Russian Science Foundation (grant №1 -1300589). References: [1] I.A. Bezkishko, A.A. Zagidullin, V.A. Milyukov, O.G. Sinyashin, Russ. Chem. Rev., 2014, 83(6), 555

Oral presentation - B18

Laterally-Functionalized Phospholes – Versatile Building Blocks for π-Conjugated Materials Xiaoming He, Thomas Wang, Thomas Baumgartner* [email protected] Department of Chemistry and Centre for Advanced Solar Materials, University of Calgary 2500 University Drive NW, Calgary, AB T2N 1N4, Canada The design of luminescent materials with well-organized one- or two-dimensional structures is gaining considerable importance for the rapidly evolving field of organic electronics. In this context, the incorporation of organophosphorus ring systems into π-conjugated materials has recently created a promising new avenue for efficiently engineering the optoelectronic properties at the molecular level.[1,2] This presentation will highlight the synthesis, properties, and practical applications of new functional phospholes that can easily be converted into luminescent soft materials via lateral functionalization at the phosphorus center. Depending on the specific architecture of the conjugated scaffold, the self-assembly properties of the materials can be turned on/off. The overall morphology of the obtained nano-/microstructures can furthermore be addressed by the degree of π-conjugation in the head group. Moreover, the functional properties of the system can also effectively be tuned by variation of the pendant group.

References: [1] T. Baumgartner, Acc. Chem. Res. 2014, 47, 1613-1622. [2] Z. Wang, T. Baumgartner, Chem. Rec. 2015, 15, 199-217.

Oral presentation - B19

From cyclic and polycyclic alkoxoaluminium hydrides to alumina composites with nano- and micro-meter rings and cages Michael Veith, Ali Awadelkareem, Hakima Smail-Bubel, Marina Martinez-Miró, Cenk Aktas, Karin Kiefer [email protected] Universität des Saarlandes und Leibniz-Institut für Neue Materialien Campus D2.2, GER-66123 Saarbrücken Alkoxoalanes of the general formula (RO)xAlH3-x may form different oligomers depending on the organic substituent R. While with R= tert-butyl the compound [(CH3)3C-O-AlH2]2 (1) is dimeric with a simple Al2O2-ring, the cyclo-pentyl derivatives show a large variety of polycyclic structures of which [H6Al4(O-C5H9)6] and [H16Al8(O-C5H9)8] are cited as examples. Treating 1 with diphenyl-silane-diol Ph2Si(OH)2 and subsequently with metal acetylacetonates (acac)2M(H2O)2 (M= Mg, Fe, Co, Ni) leads to new polycycles with disiloxane and acetylacetonate chelates of the general formula [(acac)2Al(O-SiPh2-O-SiPh2-O)]2M(H2O)2 with M= Mg, Fe, Co, Ni. These new molecular alumosilikates display two acetyl-acetonate ligands at the aluminum atoms as well as two disilatrioxy chains linking the aluminum atoms to obtain a twelve-membered (Al-O-Si-O-Si-O)2 cycle, in the centre of which the divalent metal atoms are linked through four oxygen atoms of the cycle. Thermolysis of 1 at moderate temperatures in the gas phase produces Al/Al2O3-composites which adopt different nano-structures depending on the pressure and temperature. We have recently been able to analyze the three dimensional structures of these composites by FIB-microscopy in detail and could establish ring and cage structures composed of Al/Al2O3 with reproducible nano- and mico-meter dimensions. The holes and surfaces of these structures can be used for storage of small molecules or as a sort of scaffold for living cells. In this second application either adhesion or rejection for the cell may be triggered. With certain surface modifications even preferential cell growth is obtained.1

References: 1) K. Kiefer, J. Lee, A. Haidar, M. Martinez-Miró, C.K. Akkan, M. Veith, O.C. Aktas, H. AbdulKhaliq, Nanotechnology, 2014, 25, 495101.

Oral presentation - B20

A WORLD OF DIFFERENCE – ALKALI METAL ORGANIC FRAMEWORKS FROM AMMONIA Dietmar Stalke [email protected] Institut für Anorganische Chemie der Georg-August Universität Göttingen Tammannstr. 4, 37077 Göttingen, Germany Layered structures and intercalation compounds play an outstanding role in materials science. Most prominent are graphite intercalation compounds due to their use in energy storage via Li-ion batteries. We envisage self-assemblies of charged supramolecular sandwich structures to form by polycyclic carbanions and alkali metal cations to represent structural motifs of charged anode materials in prospective rechargeable batteries. A small flat and charged building block is the indenyl anion [Ind]- and an advantageous donor base for this endeavour is ammonia. Both ammines, [Li(NH3)4][Ind] and [Na(NH3)4][Ind], contain a cation coordinated by four ammonia molecules. While the first shows the anticipated tetrahedral coordination, in the second cation the metal is unexpectedly square planar coordinated. The solvent separated ion pair forms a rippled layer structure of alternating planar Na(NH3)4+ cations and indenyl carbanions, attributed to NH3Lp hydrogen bonds (Fig. 1).[1] Those hydrogen bonds are a robust structure-determining feature, studied by means of experimental and theoretical charge density studies. The density distribution in [CpNa(NH3)3] can be considered a spectacular illustration of the structuredetermining strength of intermolecular interactions; the N–HLπ interactions are strong enough to compete with the polarising effect of the sodium cation towards the density of the cyclopentadienide ring.[2] We have shown recently that addition of ammonia to THF generates lithocene or even naked Cp anions.[3] The strong donating and deaggregating properties of ammonia observed herein are the most likely reason for the high reaction rate of many organometallics in liquid ammonia. The use of ammonia can be the key for reactions with a high potential barrier caused by steric repulsion.[4]

Figure 1. [Na(NH3)4][Ind] References: [1] Michel R., Nack T., Neufeld R., Dieterich J. M., Mata R. A. and Stalke D., Angew. Chem. 2013, 125, 762-766; Angew. Chem. Int. Ed. 2013, 52, 734-738. [2] Hey J., Andrada D. M., Michel R., Mata R. A. and Stalke D., Angew. Chem. 2013, 125, 1055510559; Angew. Chem. Int. Ed. 2013, 52, 10365-10369. [3] Michel R., Herbst-Irmer R. and Stalke, D., Organometallics 2010, 29, 6169-6171. [4] Michel R., Herbst-Irmer R. and Stalke, D., Organometallics 2011, 30, 6169-6171.

Oral presentation - B21

Coordination Polymers from Main Group Ring Compounds Saturday Amedu Okeh, René T. Boeré* [email protected] Department of Chemistry and Biochemistry, University of Lethbridge 4401 University Dr, Lethbridge, AB, Canada T1K 3M4 Coordination polymers built from bridging organic ligands are well established in the literature and have been developed for numerous applications. Much less has been reported on using main group ring compounds, which provide a rich opportunity for redox activity of the ligands.[1] Herein we report on novel results using 4,7disubstituted-2,1,3-benzothiadiazoles as bridging ligands for coordination polymers. The ligands (nitrile, ester and carboxylic acid functional groups) are prepared according to literature procedures (see Figure).[2] The synthesis, structures and properties of a number of coordination polymers of Ag(I) will be presented.

Figure 1. Synthesis of 4,7-disubstituted-2,1,3-benzothiadiazole ligands (above), displacement ellipsoids plot of the asymmetric unit in [Ag(DCBTD)]BF4 (below).

References: [1]L. R. MacGilivray, Ed., Metal-Organic Frameworks: Design and Application; Wiley: Chichester, 2010; p. 165-192. [2] (a) K. Pilgram, R. D. Skiles, J. Heterocycl. Chem., 1974, 11, 777; (b) K. Pilgram, J. Heterocycl. Chem., 1974, 11, 834.

Oral presentation - B22

Ligand Chemistry of Stable Phosphorus(I) Compounds Charles L. B. Macdonald*, Justin F. Binder, Ala'aeddeen Swidan, Stephanie M. Kosnik, Bobby D. Ellis [email protected] Chemistry & Biochemistry University of Windsor 401 Sunset Ave., Windsor, ON, N9B 3P4, Canada For more than a decade, we have been investigating the chemistry of compounds containing p-block elements in unusually low oxidation states.[1] For group 15, we have developed convenient syntheses for compounds containing donor-stabilized P(I) ions.[2] Many of these compounds (see Figure 1 for some structural depictions) are airand moisture-stable and some are valuable reagents for the synthesis of other stable low-oxidation state species using ligand replacement reactions. The univalent phosphorus atoms in such molecules resemble those of phosphanides in that they feature two pairs of non-bonding electrons that may be suitable for binding to metals or Lewis acids; several research groups have demonstrated that these molecules do indeed exhibit interesting ligand chemistry.[3] Our latest results will be presented.

Figure 1. Molecular structures of some stable P(I) compounds we investigate.

Acknowledgements: We thank NSERC, CFI, and the Government of Ontario. References: [1](a) C. L. B. Macdonald, B. D. Ellis, A. Swidan, Encyclopedia of Inorganic and Bioinorganic Chemistry, John Wiley & Sons, Ltd, 2012; (b) B. D. Ellis, C. L. B. Macdonald, Coord. Chem. Rev. 2007, 251, 936-973. [2](a) B. D. Ellis, C. A. Dyker, A. Decken, C. L. B. Macdonald, Chem. Commun. 2005, 1965-1967; (b) B. D. Ellis, C. L. B. Macdonald, Inorg. Chem. 2006, 45, 6864-6874; (c) E. L. Norton, K. L. S. Szekely, J. W. Dube, P. G. Bomben, C. L. B. Macdonald, Inorg. Chem. 2008, 47, 1196-1203. [3](a) J. W. Dube, C. L. B. Macdonald, P. J. Ragogna, Angew. Chem. Int. Ed. 2012, 51, 13026-13030; (b) J. W. Dube, C. L. B. Macdonald, B. D. Ellis, P. J. Ragogna, Inorg. Chem. 2013, 52, 11438-11449; (c) K. Schwedtmann, M. H. Holthausen, K. O. Feldmann, J. J. Weigand, Angew. Chem. Int. Ed. 2013, 52, 14204-14208; (d) S. C. Kosnik, G. J. Farrar, E. L. Norton, B. F. T. Cooper, B. D. Ellis, C. L. B. Macdonald, Inorg. Chem. 2014, 53, 13061-13069; (e) J. F. Binder, A. Swidan, M. Tang, J. H. Nguyen, C. L. B. Macdonald, Chem. Commun. 2015, in press.

Oral presentation - B23

THERMOCHROMIC EMISSIVE METALLACYCLES Lescop. C.,*(a) El Sayed Moussa. M.,(a) Evariste. S.,(a) Wong. H-L.,(b) Le Bras. L.,(c) Le Guennic. B.,(c) Costuas. [email protected] (a) Phosphore et Matériaux Moléculaires, UMR 6226 CNRS-Université de Rennes 1 Campus de Beaulieu, 35042 Rennes Cedex, France (b) Department of Chemistry, University of Hong Kong, Hong Kong, Chine (c) Chimie Théorique et Inorganique ISCR Thermochromic luminescent derivatives constitute a peculiar class of emissive materials whose emission varies with temperature.[1] To date, the most remarquable class of such derivatives is mostly based on Cu4I4 cubane cores.[1c-e] Using a very general supramolecular chemistry synthetic approach previously developped in our group,[2] a new series of polymetallic Cu(I) metallacycles Cu n (n= , , 12, ∞) has been recently obtained. Their syntheses, solid state caracterizations will be presented together with their themochromic emissive behaviors and TD-DFT calculations aimed to understand the electronic structure of these derivatives.

Acknowledgements: The ANR (France) and the RGC (Hong Kong) (projet ANR-RGC Int. POPTOELECTR-MOLMAT), the Humboldt Foundation, the Ministère de la Recherche et de l’Enseignement Supérieur and the CNRS are thanked. References: [1] a) J. Feng, K. J. Tian, D. H. Hu, S. Q. Wang, S. Y. Li, Y. Zeng, Y. Li, G. Q. Yang, Angew. Chem. Int. Ed. 2011, 50, 8072; b) F. M. Ye, C. F. Wu, Y. H. Jin, Y. H. Chan, X. J. Zhang, D. T. Chiu, J. Am. Chem. Soc. 2011, 133, 8146; c) H.D. Hardt, A.Z. Pierre, Z. Anorg. Allg. Chem., 1973, 402,107; d) S. Perruchas, C. Tard, X. F. Le Goff, A. Fargues, A. Garcia, S. Kahlal, J-Y. Saillard, T. Gacoin, J. P. Boilot, Inorg. Chem, 2011, 50, 10682; e) D. Sun, S. Yuan, H. Wang, H-F. Lu, S-Y. Feng, D-F. Sun, Chem. Commun., 2013, 49, 6152; f) K. Miyata, Y. Konno, T. Nakanishi, A. Kobayashi, M. Kato, K. Fushimi, Y. Hasegawa, Angew. Chem. Int. Ed. 2013, 52, 6413. [2] a) B. Nohra, S. Graule, C. Lescop, R. Réau, J. Am. Chem. Soc. 2006, 128, 3520; b) B. Nohra, Y. Yao, C. Lescop, R. Réau, Angew. Chem. Int. Ed., 2007, 46, 8242; c) Y. Yao, W. Shen, B. Nohra, C. Lescop, R. Réau, Chem. Eur. J. 2010, 16, 7143; d) V. Vreshch, W. Shen, B. Nohra, S-K Yip, V.W-W. Yam, C. Lescop, R. Réau, Chem. Eur. J., 2012, 2, 466; e) M. El Sayed Moussa, K. Guillois, W. Shen, R. Réau,J. Crassous, C. Lescop, Chem. Eur. J., 2014, 20, 14853.

Oral presentation - B24

Paving the Way to Novel Phosphorus-based Architectures: a Noncatalyzed Protocol to Access Fused Heterocycles Carlos Romero-Nieto, Alicia ópez-Andarias, Carolina Egler-Lucas, Florian Gebert, Jens-Peter Neus, Oliver Pilgram [email protected] Organisch-Chemisches Institut, University of Heidelberg Im Neuenheimer Feld 270, Room 270a, GER-69120, Heidelberg Opening up new horizons into materials science requires the development of novel architectures. To that end, phosphorus heterocycles provide a wide set of unique possibilities. Thus, the singular hybridization of phosphorus centers enables a series of reversible post-functionalization reactions.[1] The latter allow: a) tailoring the optoelectronic properties to specific applications and, b) adjusting the intermolecular interactions to access intriguing phenomena such as piezochromism,[2] thermochromism[3] and liquid crystallinity[3] among others. To exploit the aforementioned features into materials science, a great deal of research efforts has been invested in providing new synthetic routes to prepare phosphorus heterocycles.[4] Currently, however, synthetic protocols to access π-extended phosphorus-based structures still remain scarce. In this communication, I present a new non-catalyzed synthetic protocol to obtain novel, fused phosphorus heterocycles. The scope of this reaction reveals a great potential to access superior π-extended systems. Postfunctionalization reactions either at the main scaffold or at the phosphorus center bring about a series of unusual optoelectronic properties. Altogether, our phosphorusbased architectures introduce new opportunities into the field of functional materials.

Acknowledgements: Financial support by the Fonds der Chemischen Industrie, Germany, is gratefully acknowledged. We also thank the Organisch-Chemisches Institut, Universität Heidelberg, Germany, for its support. References: [1] T. Baumgartner, Acc. Chem. Res., 2014, 47, 1613-1622. [2] Y. Ren, W. H. Kan, M. A. Henderson, P. G. Bomben, C. P. Berlinguette, V. Thangadurai, T. Baumgartner, J. Am. Chem. Soc. 2011, 133, 17014-17026. [3] C. Romero-Nieto, M. Marcos, S. Merino, J. Barberá, T. Baumgartner, J. Rodríguez-López, Adv. Funct. Mater. 2011, 21, 4088-4099. [4] (a) K. Baba, M. Tobisu, N. Chatani, Angew. Chem. Int. Ed. 2013, 52, 1-5; (b) Y. Kuninobu, T. Yoshida, K. Takai, J. Org. Chem. 2011, 76, 7370-7376; (c) S. Furukawa, S. Haga, J. Kobayashi, T. Kawashima, Org. Lett. 2014, 16, 3228-3231.

Oral presentation - B25

Photoinduced Rearrangement of Acylcyclopolysilanes Harald Stueger, Michael Haas, Bernd Hasken, Roland Fischer, Michaela Flock, Martin Rausch, Lukas Schuh, Ana Torvisco [email protected] Institute of Inorganic Chemistry, Graz University of Technology Stremayrgasse 9, 8010 Graz, Austria Only selected examples of stable Si=C bonded species with Si-Si bonds and the unsaturated silicon atom incorporated into cyclic structures have been synthesized so far.[1] Thus, previously unknown acylcyclohexasilanes (Me3Si)2Si6Me8(Me3Si)COR (1; R = alkyl, aryl) have been synthesized and their photochemical rearrangement reactions have been studied.[2] When photolyzed with λ > 300 nm radiation alkyl substituted type 1 compounds showed Brook type 1,3-Si→O migration reactions to generate the cyclohexasilanes 2 with exocyclic Si=C bonds along with smaller amounts of the ring enlarged species 3 with endocyclic Si=C double bonds. While 2 was stable enough to allow characterization by NMR and UV absorption spectroscopy the less stable products 3 could only be observed in form of their methanol adducts. With an o-tolyl-group attached to the carbonyl C atom under the same conditions 1 exclusively underwent ring scission adjacent to the Si-C=O moiety followed by 1,3Si→O migration of the resulting terminal SiMe2group to give the endocyclic product 3 with remarkable selectivity, which could be isolated and fully characterized.

Figure 1. Photochemical rearrangement of acylcyclohexasilanes.

References: [1] H. Ottosson, A. M. Eklöf, Coord. Chem. Rev. 2008, 252, 1287. [2] (a) H. Stueger, B. Hasken, M. Haas, M. Rausch, R. Fischer, A.Torvisco, Organometallics 2014, 33, 231. (b) M. Haas, R. Fischer, L. Schuh, R. Saf, A. Torvisco, H. Stueger, Eur. J. Inorg. Chem. 2015, 997.

Oral presentation - B26

Cyclodiphosphazanes in Metal Organic Frameworks Maravanji S. Balakrishna Mujahuddin M. Siddiqui Guddekoppa S. Anantnag [email protected] Department of Chemistry Phosphorus Laboratory, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India The coordination chemistry of cyclodiphosphazanes or diazadiphosphetidines has been extensively studied in recent years and this is mainly due to the generation of several interesting derivatives with donor functionalities. However, the utility of either bisphosphanes or cyclodiphosphazanes in designing homolyptic metal organic frameworks is scarce. This may be due to the non-availability of suitable linkers with rigid frameworks (such as 4,4’-bipyridine) as the pyramidal geometry at the phosphorus atom and free rotation about the P–C bonds allow a range of accessible orientations of lone pairs bringing a disambiguity in the coordination behavior. In this context, we have designed structurally more rigid cyclodiphosphazanes and explored their rich transition metal chemistry. In this talk, a few such systems will be discussed

Figure 1: Copper(I)-Cyclodiphosphazanes Complexes with Sodalite and Dimonodoid Structures

Acknowledgements: This work is supported by a grant SR/S1/IC-17/2014 from De-partment of Science and Technology (DST), New Delhi, India. We are thankful to Prof. Joel T. Mague, Tulane University, New Orleans, for X-ray structure determination. References: [1] M. M. Siddiqui, S. M. Mobin, I. Senkovska, S. Kaskel, M.S. Balakrishna, Chem. Commun. 2014, 50 12207-12209. [2] M.M. Siddiqui , J. T. Mague, M. S. Balakrishna, Inorg. Chem. 2015, 54, 1200-1202. [3] G.S. Ananthnag , J.T. Mague, M.S. Balakrishna, Dalton Trans. 2015, 44, 3785-3793.

Oral presentation - B27

Complexes Containing W≡E (E = P, As and Sb) Triple Bond as Precursors for Linearly Coordinated EQ (Q = O, S, Se and Te) Ligands Gábor Balázs, Manfred Scheer [email protected] Institute of Inorganic Chemistry, University of Regensburg Universitätsstraße 31, GER-93053, Regensburg The coordination chemistry of nitrogen monoxide (NO) was extensively studied in the early 70s. This versatile ligand can adopt a wide range of bonding motifs in transition metal complexes. In contrast, the coordination chemistry of the heavier homologues is less studied. This is partly due to the unavailability of the free EQ (E = P, As, Sb, Bi; Q = S, Se, Te) ligands as well as to their poor coordinating abilities. The majority of known transition metal EQ complexes contains PQ (Q = O, S, Se) ligands that are coordinated to three metal centers in a μ3 fashion. The synthesis of the isolable terminal pnictido complexes [(N3N)W≡E] [N3N=N(CH2CH2NSiMe3)3; E = P, As, Sb][1] made the synthesis of complexes containing η1-EQ ligands accessible. Our interest was oriented toward the synthesis and reactivity studies of complexes containing linear EQ ligands. The oxidation of [(N3N)W≡E] (E = P, As) with chalcogenes or suitable calcogene sources leads to the formation of the corresponding [(N3N)W(η1-EQ)] complexes (Equation 1; Figure 1).[2] Quantum chemical calculations show that the bonding in the W–E–Q unit is best described by two polarized double bonds.[3] An overview of the reactivity of [(N3N)W(η1-EQ)] complexes will be presented.

Figure 1. Synthesis and Molecular structure of [{(Me3SiNCH2CH2)3N}W(η1-PTe)]. H atoms omitted for clarity. References: [1] a) R. R. Schrock, N. C. Zanetti, W. N. Davis Angew. Chem. Int. Ed. Engl. 1995, 34, 2044; b) M. Scheer, J. Müller, M. Häser Angew. Chem. 1996, 108, 2637; c) G. Balázs, M. Sierka, M. Scheer Angew. Chem. Int. Ed. 2005, 44, 4920. [2] Balázs, G.; Green, J. C.; Scheer, M. Chem. Eur. J. 2006, 12, 8603-8608. [3] Balázs, G.; Green, J. C.; Mingos, D. M. P. Eur. J. Inorg. Chem. 2007, 2443-2453.

Oral presentation - C01

Is Single-4-Ring the Most Basic but Elusive Secondary Building Unit that Transforms to Larger Structures in Zinc Phosphate Chemistry? Ramaswamy Murugavel [email protected] Indian Institute of Technology Bombay, Powai, Mumbai 400076, India Our laboratory has been using an organophosphate monoester (ArO)P(O)(OH) (Ar = 2,6-diisopropylphenyl) as the primary building unit (PBU) to assemble polyhedral molecules that resemble one or more zeolite secondary building units and display various functions.1-4 The reaction of this PBU with a divalent metal ion such as Zn2+ in a donor solvent leads to the isolation of stable tetranuclear metal phosphates [(ArO)PO3Zn(L)]4 build around a Zn4O12P4D4R SBU core. In recent times we have unraveled that it is also possible to isolate other SBUs, starting from the same set of reactants, but by making small variations in the reaction conditions. Now it is possible to isolate hitherto unknown discrete D6R and D8R SBUs (which possess Zn6O18P6 and Zn8O24P8 cores, respectively) by switching the solvent from methanol to acetonitrile and the co-ligand from DMSO to either 3-formylpyridine5 or 4cyanopyridine.6 Irrespective of the conditions employed, S4R SBUs are formed as the initial products. By co-existence of free phosphoryl groups and coordinative unsaturation at zinc, these S4R SBUs aggregate. The explanation for the formation of larger SBUs such as D6R and D8R from a S4R however would need a two-stage mechanism involving (a) side-by-side fusion of two or more S4Rs and (b) a constructive folding to close up the double-n-ring (n = 4, 6, or 8) SBUs. One cannot discount the possibility of misfolding in step (b), which will lead to the isolation of polymeric chains with a staircase conformation.

Figure 1. Single-4-Ring, the basic structural unit References: 1. Kalita, A.C.; Roch-Marchal, C.; Murugavel, R. Dalton Trans., 2013, 26, 9755. 2. Kalita, A.C.; Murugavel, R. Inorg. Chem., 2014, 53, 3345. 3. Kalita, A.C.; Gogoi, N.; Jangir, R.; Kupuswamy, S.; Walawalkar, M. G.; Murugavel, R. Inorg. Chem., 2014, 53, 8959. 4. Kalita, A.C.; Sharma, K.; Murugavel, R. Cryst. Eng. Comm. 2014, 16, 51. 5. Gupta, S.K.; Dar, A. A.; Rajeshkumar, T.; Kuppuswamy, S.; Langley, S. K.; Murray, K. S.; Rajaraman, G.; Murugavel, R. Dalton Trans. 2015, 44, 5587. 6. Gupta, S.K.; Kuppuswamy, S.; Walsh, J. P. S.; McInnes, E. J. L.; Murugavel, R. Dalton Trans. 2015, 44, 5961. 7. Dar, A.; Sharma, S. K. Murugavel, R. Inorg. Chem. 2015, in press.

Oral presentation - C02

NHC Ligands for Ternary Metal-Chalcogen Cluster Assembly Mahmood Azizpoor Fard, Bahareh Khalili Najafabadi, John F. Corrigan* [email protected] Department of Chemistry, The University of Western Ontario 1151 Richmond St, London, N6A 5B7, Canada Ligand stabilized metal-trimethylsilylchalcogenolates [LnM-ESiMe3] (L = PR3; E = S, Se, Te; M = Cu, Ag) offer routes for the controlled formation of several ternary M-EM´ clusters when these coordination complexes are reacted with a second metal salt. This arises from the reactivity of the chalcogen-silicon bond in M-ESiMe3 and the complexes serving as a soluble source of “metallachalcogenolate”, ME–. Using Nheterocyclic carbenes (NHC) as ancillary ligands in this class of complex, we set out to increase the thermal stability of M-ESiMe3with improved control of reactivity during ternary MM´E cluster formation. The preparation of a series of NHC ligated copper-chalcogenolate complexes of the general formula [(IPr)Cu-ESiMe3] (IPr = 1,3bis(2,6-diisopropylphenyl)imidazolin-2-ylidene; E = S, Se, Te) will be described. These are prepared selectively in high yield with demonstrated utility as precursors for ternary MM´E. The reaction of [(IPr)Cu-SSiMe3] with mercuric(II) acetate affords the complex [{(IPr)CuS}2Hg] (1) containing two (IPr)Cu-S- fragments bonded to a central Hg(II) (see Figure 1).[1] The synthesis of the isostructural silver complexes, [(IPr)Ag-ESiMe3] (E = S, Se) and their reactivity toward metal salts will be also presented. Using the smaller NHC ligand 1,3-di-isopropylbenzimidazole-2-ylidene (iPr2-bimy), the preparation of such stable Cu-ESiMe3 (E = S, Se) is also possible, and X-ray analysis illustrates that these exist as the dimers [(iPr2-bimy)2Cu2(μ-ESiMe3)2] in the solid state. The reactivity of these molecules for the formation of ternary clusters will be described and compared to that of [(IPr)Cu-ESiMe3].

Figure 1. Molecular Structure of 1.

References: [1] M. Azizpoor Fard, F. Weigend, J. F. Corrigan, Chem. Commun, 2015, DOI: 10.1039/c5cc00940e.

Oral presentation - C03

Reactivity and Structure-Building Principles of LiCKOR Base Mixtures in THF Ulrike Kroesen, Stephan G. Koller, Kathrin Louven and Carsten Strohmann* [email protected] Faculty of Chemistry and Chemical Biology, TU Dortmund University Otto-Hahn-Str. 6, Ger-44227, Dortmund The iC OR superbase or “Schlosser’s base” constitutes an important component in the tool kit of organometallic chemists.[1] It is comprised of a mix of an alkyllithium reagent, usually n-butyllithium (“ iC”), and a bulky alkoxide of a heavier alkaline metal, typically potassium tert-butoxide (“ OR”). Their metalating power exceeds that of their single components by far. This synthetically well exploited synergic increase in reactivity has recently attracted our interest as the successful structural elucidation of species arising from LiCKOR mixtures, especially in the commonly used polar solvent THF, remains a challenge.[2] Herein, we present the structures of the species formed from reaction mixtures containing LiCKOR components and substrates which undergo metalation by this base mix even at –78 °C in THF. Furthermore, the synthetic value of a Schlosser’s base-mediated metalation under mild conditions was demonstrated using dimethylphenethylamine.[3] This pharmaceutically attractive synthetic building block can be selectively metalated in the benzylic position by LiCKOR mixtures at low temperatures. Thus, decomposition of the ß-metalated intermediate via elimination is efficiently avoided and its conversion with electrophiles can be achieved.

Acknowledgements: We are grateful to the Deutsche Forschungsgemeinschaft (DFG) and the Fonds der Chemischen Industrie (FCI) for financial support References: [1] a) M. Schlosser, Angew. Chem. Int. Ed. 2005, 44, 376–393; b) L. Lochmann, Eur. J. Inorg. Chem. 2000, 1115–1126; c) M. Schlosser, Pure Appl. Chem. 1988, 60, 1627–1634. [2] a) S. Harder; A. Streitwieser, Angew. Chem. Int. Ed. Engl. 1993, 1066–1068; b) A. R. Kennedy; J. G. MacLellan; R. E. Mulvey, Angew. Chem. Int. Ed. 2001, 40, 3345–3347. [3] a) C. Unkelbach; H. S. Rosenbaum; C. Strohmann, Chem. Commun. 2012, 48, 10612–10614; b) C. Unkelbach, D. F. O'Shea, C. Strohmann, Angew. Chem. Int. Ed. 2014, 53, 553–556.

Oral presentation - C04

Functional metal-organic molecules and materials derived from rigid and flexible P-N scaffolds Ramamoorthy Boomishankar* [email protected] Department of Chemistry, Indian Institute of Science Education and Research (IISER), Pune Dr. Homi Bhabha Road, Pune - 411008, India Employing phosphoramide ligands of formula, (RNH)3PO in reaction with Pd(OAc)2, a facile route to access the highly basic trianions, [(RN)3PO]3‒ ((X)3‒) analogous to PO43− ion was developed. The (X)3‒ ligand, containing a central binding group, acts as a rigid cis-blocking ligand and stabilizes trimeric or prismatic Pd(II) cluster of formula {Pd3X(OAc)3}1or2.[1] Further, the trinuclear (Pd3X)3+ motifs have been utilized as supramolecular synthons for obtaining neutral cluster cages for Pd(II) ions in tetrahedral and cubic topologies via a bridging ligand substitution strategy.[2] In contrast, phosphoramides containing peripheral metal binding groups provide a flexible ligand platform and yield multi-metallic assemblies in various dynamic architectures.[3] By using 3-pyridyl functionalized dipodal phosphoramide ligand (L) we were able to generate interesting examples of Cu IIL2 frameworks that show anion dependent structure and ferroelectric behaviour.[4]

Figure 1. (a) Formation of a neutral tetrahedral cage, and its selective guest uptake behaviour; (b) Anion driven Cu(II) assemblies and their structure dependent physical properties.

Acknowledgements: This work was supported by IISER, Pune and the SERB, DST, India through Grant No. SR/S1/IC-50/2012. References: [1] A. K. Gupta, S. A. D. Reddy and R. Boomishankar, Inorg. Chem. 2013, 52, 7608. [2] A. K. Gupta, A. Yadav, A. K. Srivastava, K. R. Ramya, H. Paithankar, S. Nandi, J. Chugh and R. Boomishankar, Inorg. Chem. 2015, 54, DOI: 10.1021/ic502798r. [3] (a) A. K. Gupta, S. S. Nagarkar and R. Boomishankar Dalton Trans. 2013, 42, 10964; (b) A. K. Gupta, A. K. Srivastava, I. K. Mahawar and R. Boomishankar Cryst. Growth Des. 2014, 14, 1701. [4] A. K. Srivastava, B. Praveen Kumar, I. K. Mahawar, P. Divya, S. Shalini and R. Boomishankar Chem. Mater. 2014, 26, 3811.

Oral presentation - C05

Chlorine/oxygen transfer reactions of [PCl2N]3 using oxygenated Lewis bases as a possible route to [PON]3 Benjamin S. Thome, Savannah R. Snyder, Joanna M. Beres, Patrick O. Wagers, Matthew J. Panzner, Brain D. Wright, Wiley J. Youngs, Claire A. Tessier* [email protected] Department of Chemistry, University of Akron 190 E Buchtel Commons, Akron, OH, 44325-3601, USA The reactions of [PCl2N]3 with a variety of oxygen containing Lewis bases (O=E = HMPA, OPEt3 and DMF) result in Cl/O exchange. The reactions occur via a two-step process (Fig. 1) which involves 1) formation of an intermediate salt [P3N3Cl5O] [E-Cl]+ and 2) attack by O=E to form P3N3Cl4O-O=E and [E-Cl]+[Cl]-. In addition to spectral characterizations, both phosphazene products of the HMPA reactions have been characterized by X-ray crystallography. As shown by reaction chemistry and the Gutmann-Beckett Lewis acidity scale, the P=O of the phosphazene ring in P3N3Cl4O-O=E has a strong Lewis acid character. We are investigating the use of more vigorous reaction conditions, other O=E and metal catalysis to promote the types of reactions in Fig. 1 on all the P atoms of the phosphazene ring with the goal of preparing [PON]3 or its base-stabilized adducts. Such molecules could be precursors to novel PNO materials

Acknowledgements: We thank ICL and OMNOVA Foundation for support of this work.

Oral presentation - C06

Phosphorus heterocycles from Na(OCP) Zoltán Benkő, Dominikus Heift, Hansjörg Grützmacher [email protected] Department of Inorganic and Analytical Chemistry, Budapest University of Technology and Economics Szent Gellért tér 4. H-1111, Budapest Sodium phosphaethynolate, Na(OCP), has been shown to be a simple and easily accessible one-phosphorus building block for transition metal complexes and heterocycles, furthermore, it can also undergo nucleophilic reactions and cycloadditions. As it will be presented, Na(OCP) reacts with two equivalents of dicyclohexylcarbodiimide (DCC) to yield an anionic, imino-functionalized 1,3,5diazaphosphinane, shown on the left in the figure below. The oxidation of this anion with elemental iodine causes an intramolecular rearrangement reaction to give a bicyclic 1,3,2-diazaphospholenium cation (depicted on the right). The “Umpolung” of the electronic properties from non-aromatic to highly aromatic is reversible and the cation is reduced with elemental magnesium to give back the 1,3,5diazaphosphinanide anion. High level theoretical calculations on the reaction mechanisms suggest that phosphinidene species are involved in the rearrangement processes.[1]

Figure 1. The chemically reversible redox triggered interconversion of the monocyclic anion and the bicyclic cation

References: [1] D. Heift, Z. Benkő, H. Grützmacher, Angew. Chem. Int. Ed., 2014, 53, 6757-6761

Oral presentation - C07

Terpene Main Group Chiral Derivatives: Catalytic Activity in Polymerization and C-H Activation Processes Marta E. G. Mosquera,* María Fernández-Millán, Ghaita Chahboun, Jesús Cano, Tomás Cuenca [email protected] Department of Organic Chemistry and Inorganic Chemistry Alcalá University, Campus Universitario, 28805-Alcala de Henares, Madrid. Spain Chiral catalysts have provided very efficient systems that allow the preparation of enantiomerically pure derivatives. Interestingly, the number of well-defined main group complexes described with chiral ligands is remarkably lower than the transition metal counterparts, even though main group coordination compounds are active in a variety of important catalytic processes.[1] In this context, one of our ongoing research areas is focused on the preparation of homo and heterometallic aluminium complexes with O- and N- donor ligands and the study of their activity in catalytic polymerization processes.[2] We have extended these studies to O- and N- donor chiral ligands using naturally occurring compounds. In particular, we used terpenoids since they are excellent ligand precursors.[3] From them it is possible to prepare multifunctional pro-ligands, by adding an extra functional group such as an alcohol or an oxime moiety. These multifunctional molecules can furnish polymetallic chiral coordination compounds by the reaction with the appropriate metallic precursors. These studies have led us to prepare new chiral derivatives with unusual structures, which are active in catalytic ROP polymerization processes and also in the activation of C-H bonds in carbonyl compounds.

Figure 1. Terpene based aluminium heterometallic chiral compound

References: [1] The Renaissance of Main group Chemistry; Themed Issue, Dalton Transactions, 2008, 4321. [2] (a) G. Martínez, J. Chirinos, M. E. G. Mosquera, T. Cuenca, E. Gómez, Eur. J. Inorg. Chem, 2010, 1522; (b) V. Tabernero, M. E. G. Mosquera, T. Cuenca, Organometallics, 2010, 29, 3642; (c) G. Martínez, M. E. G. Mosquera, T. Cuenca, Eur. J. Inorg. Chem, 2012, 3611; (d) García-Valle, F. M.; Estivill, R.; Gallegos, C.; Cuenca, T.; Mosquera, M. E. G.; Tabernero, V.; Cano, J. Organometallics 2015, 34, 477. [3] M. S. Ibn El Alami, M. A. El Amrani, F. Agbossou-Niedercorn, I. Suisse, A. Mortreux, Chem. Eur. J. 2015, 21, 1398.

Oral presentation - C08

Reactions of Aryl and Hetaryl Thioketones with Pt(0) Complexes; Ferrocenyl Substituted Platinathiiranes Grzegorz Mlostoń (a), Sebastian Gröber (b), Wolfgang Weigand (b) [email protected] a) Department of Organic & Applied Chemistry, University of Łódź, PL-91-403 Łódź, Tamka 12, Poland b) Institute of Inorganic & Analytical Chemistry, University of Jena, D-07743 Jena, Humboldtstr. 8, Germany In a series of recent publications, reactions of 1,2,4-trithiolanes with L2Pt(0) complexes (L2= bisphosphane), leading to the formation of platinathiiranes 1, side by side with dithiolato complexes 2, were reported.[1] On the other side, heterocycles 1 can be prepared in high yields by treatment of aromatic and cycloaliphatic thioketones with Pt(0)-phosphine complexes in toluene solution.[2] In our ongoing studies on the chemistry of thiocarbonyl compounds, a series of new aryl/hetaryl thioketones, including representatives bearing ferrocenyl moiety, was prepared and successfully applied as novel building blocks for the synthesis of sulfur heterocycles with variable ring size. In the communication, reactions of aryl/hetaryl thioketones 3 with L2Pt(0) complexes, leading to new derivatives of platinathiiranes 1 will be presented. Molecular structures of isolated products were established by means of spectroscopic methods, and in some cases confirmed by using the X-ray crystallography.

Acknowledgements: The authors thank the National Science Center (Cracow, Poland) for financial support within the grant Maestro (Grant Maestro-3 (Dec-2012/06/A/ST5/00219) References: [1] a) T. Weisheit, A. Kriltz, H. Görls, G. Mloston, W. Imhof, W. Weigand, Chem. Asian J. 2012, 7, 1383; b) H. Petzold, S. Brätigam, H. Görls, W. Weigand, M. Celeda, G. Mloston, Chem. Eur. J. 2006, 12, 8090. [2] W. Weigand, R. Wünsch, C. Robl, G. Mloston, H. Nöth, M. Schmidt, Z. Naturforsch. 2000, 55b, 453.

Oral presentation - C09

Poster Presentations

Photocyclization of Dimesitylborylarenes Naoki Ando, Tomokatsu Kushida, Aiko Fukazawa, Shuhei Iyoyama, Yoshihito Shiota, Kazunari Yoshizawa, and Shigehiro Yamaguchi [email protected] Graduate School of Science, Nagoya University, Institute for Materials Chemistry and Engineering, Kyushu University, Institute of Transformative Bio-Molecules, Nagoya University Furo, Chikusa, Nagoya 464-8602, Japan 744 Motooka, Nishi-ku, Fukuoka 819-0395, Japan The isosterism of tri-coordinated boron and carbocation imparts intriguing reactivity and properties to boron-containing π-conjugated systems. We have recently reported a new mode of photoreaction for tri-coordinate organoboron compounds, which is the bora-Nazarov cyclization of a 9-dimesitylboryl-substituted dibenzoborepin.[1] In the course of study on the substrate scope of the bora-Nazarov cyclization, we found that dimesitylboryl-substituted thiophene underwent a new mode of photoreaction to produce a spirocyclic boraindane in good yield. To gain insight into this reaction, theoretical calculations were conducted, which suggest that this new photoreaction proceed through a [1,6] sigmatropic H-rearrangement to form a biradical intermediate, followed by the intramolecular radical coupling to afford the spirocyclic product. The study on the substrate scope showed that this reaction has generality and a series of dimesitylboryl-substituted arenes undergo this photoreaction exclusively instead of the bora-Nazarov cyclization.

References: [1] A. Iida, S. Saito, T. Sasamori, S. Yamaguchi, Angew. Chem. Int. Ed. 2013, 52, 3760.

Poster presentation - P001

Chelating bis(diazaboryl) ligands for preparation of cyclic bisboryl complexes Eugene L. Kolychev, Rémi Tirfoin, Simon Aldridge* [email protected] Inorganic Chemistry Department, University of Oxford Chemistry Research Laboratory, Mansfield road 12, OX1 3TA, Oxford Recent reports by Yamashita and Nozaki et al. on the isolation[1] and reactivity[2] of the first stable boryllithium reagent have opened new possibilities for the application of diazaboryl fragments as strong σ-donor anionic ligands. Preliminary studies conducted in our laboratory showed that diazaboryl complexes of Main Group elements[3] are encouraging candidates as transition metal free bond activation reagents. Further investigation is currently focused on the preparation of bifunctional boryl ligands, with the aims (i) of increasing the stability of complexes by the chelate effect, and (ii) of facilitating re-reduction to lower oxidation states due to the presence of constrained ring systems with appropriately narrow bite angles. Synthetically, key precursors for such chelate systems are bis(diazaboryl) dibromides which can be prepared by high yielding procedures starting from commercially available starting materials. In subsequent steps, a range of approaches including metathesis using alkali metal boryl complexes and oxidative insertion of low valent metal centres into B-H bonds of the analogous boryl hydrides have been examined to establish reliable synthetic routes to chelating boryl complexes.

Figure 1. Cyclic bis(diazaboryl) complexes.

Acknowledgements: ELK gratefully acknowledges financial support by the FP7-Marie Curie IEF grant 626441. References: [1] Y. Segawa, M. Yamashita, K. Nozaki, Science, 2006, 314, 113. [2] Y. Segawa, Y. Suzuki, M. Yamashita, K. Nozaki, J. Am. Chem. Soc., 2008, 130, 16069. [3] (a) A.V. Protchenko, K. Hassomal Birjkumar, D. Dange, A.D. Schwarz, D. Vidovic, C. Jones, N. Kaltsoyannis, P. Mountford, S. Aldridge, J. Am. Chem. Soc., 2012, 134, 6500. (b) A.V. Protchenko, D. Dange, A.D. Schwarz, M.P. Blake, C. Jones, P. Mountford, S. Aldridge, J. Am. Chem. Soc., 2014, 136, 10902. (c) A.V. Protchenko, M.P. Blake, A.D. Schwarz, C. Jones, P. Mountford, S. Aldridge, Organometallics, 2015, in press, DOI:10.1021/om501252m

Poster presentation - P002

Synthetic Applications of Borylzinc Compounds: Boryl Transfer Chemistry and Catalytic Borylation. Jesús Campos, Simon Aldridge* [email protected] Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, United Kingdom Since the groundbreaking isolation of the first boryllithium species by Yamashita and Nozaki,[1] the chemistry of boryl nucleophiles has rapidly expanded. Interestingly, the reactivity of the boryl anion is highly dependent on its metallic counterion. For instance, the behaviour of a diaminosubstituted boryllithium and its magnesium analogue when added to benzaldehyde is highly dissimilar,[2] with the former leading to borylbenzylalcohol and the latter to benzoylborane. Considering the rich chemistry of alkyl zinc reagents in synthetic applications and the growing interest in zinc as an inexpensive and environmentally benign metal in catalysis, we decided to explore the still undeveloped chemistry of borylzinc compounds (A in Figure 1). [Figure 1] Transmetalation reactions using borylzinc species allowed us to synthesize a number of Transition Metal and Main Group metal boryl complexes with considerably higher yields and increased selectivity when compared to the commonly used boryllithium analogues. More interestingly, the direct use of borylzinc precursors for crosscoupling processes resulted in the borylation of a plethora of organic halides and pseudohalides, including unactivated alkyl halides, in high yields, with high functional group tolerance and under mild conditions.

Figure 1. Synthetic applications of borylzinc compounds

Acknowledgements: JC thanks Agencia Andaluza del Conocimiento (Spain) and European Commission for a Talentia Postdoc/Marie Curie Fellowship. References: [1] Y. Segawa, M. Yamashita, K. Nozaki, Science, 2006, 314, 113. [2] M. Yamashita, Y. Suzuki, Y. Segawa, K. Nozaki, J. Am. Chem. Soc. 2007, 129, 9570.

Poster presentation - P003

Well-Defined Boralumoxanes as Convenient MAO Modelling Compounds Harmen S. Zijlstra, Sjoerd Harder* [email protected] Deparment of Pharmacy and Chemistry, University of Erlangen-Nürnberg Egerlandstrasse 1, 91058 Erlangen Ever Since its serendipitous discovery methylalumoxane (MAO) has grown from an academic curiosity to an industrial commodity. Despite its importance as an activator in homogeneous polymerization catalysis its exact structure and working mechanism remain debated.1 Isolobal exchange of a "MeAlO2" unit in MAO for a "RBO2" moiety can lead to defined model compounds that still maintain their activating capabilities. Such a boralumoxane has been obtained by Hessen et al.2 Upon reaction of tBu3Al with a boronic acid (DIPP)B(OH)2 a well-defined tetrameric cluster was obtained (Scheme 1). The obtained complex could be fully characterized and was shown to be able to activate simple ziroconene precatalysts.3 Using the same principle we have expanded the scope of boronic acids used and synthesized several new, well-defined complexes. Depending on the boronic acid substituent and the B:Al ratio used a variety of different boralumoxanes can be obtained. These clusters are capable of activating simple ziroconocene precatalysts in various ways that depend on their structure. Due their structural variety and activating capabilities these boralumoxanes provide insight into the structure and possible activation mechanisms of MAO.

Scheme 1. Synthesis of a well-defined boralumoxane (Ar= 2,6-di-iPr-Phenyl; DIPP)

Acknowledgements: This research forms part of the reserach program of the Dutch Polymer Institute (DPI), projects #310 and #728 References: 1) H. S. Zijlstra, S. Harder, Eur. J. Inorg. Chem. 2015, 1, 19-43. 2) B. Richter, A. Meetsma, B. Hessen, J. H. Teuben, Chem. Comm. 2001, 14, 1286-1287. 3) B. Richter, A. Meetsma, B. Hessen, J. H. Teuben, Angew. Chem. Int. Ed. 2002, 41, 2166-2169.

Poster presentation - P004

Syntheses, structural characterization and DFT investigations of pentaborate salts templated by substituted pyrrolidinium cations Charlotte L. Jones,(a) Michael A. Beckett,(a) R. Andrew Davies,(a) Peter N. Horton(b) [email protected] School of Chemistry (a) Bangor University, Bangor, Gwynedd, LL57 2UW, UK; (b) University of Southampton, Southampton, SO17 1BJ, UK Non-metal pentaborate derived materials could be seen as alternatives to B2O3 for hydrogen storage; B2O3has been proposed as a potential hydrogen store[1] which meets the US Department of Energy's requirements of being capable of storing 6% wt. H2. A series of pentaborate salts have been synthesized, containing substituted pyrrolidinium cations. Characterizations were carried out using spectroscopic and Xray diffraction methods. Thermal properties were determined using TGA; condensation of the pentaborate network occurs between 200-300°C, before formation of B2O3 at 600°C. All compounds show extensive supramolecular H-bonded anionic lattices. H-bond interactions and motifs found in these and in other pentaborate structures have been examined and modelled by DFT calculations, confirming that Hbonds interactions in pentaborates are moderately strong (ca. −10 to −21 kJ mol−1) and are likely to dominate the energetics of their templated syntheses[2].

Figure 1. Diagrams of the (a) pyrrolidinium cations and (b) the pentaborate1− anion, as found within the synthesized salts.

References: [1] S.H. Jhi, Y.K. Kwon, K. Bradley, J.C.P. Gabriel, Solid State Commun., 2004, 129, 769-773. [2] M.A. Beckett, S.J. Coles, R.A. Davies, P.N. Horton, C.L. Jones, Dalton Trans., 2015, 44, in press, published online 10th March 2015, DOI: 10.1039/c5dt00248f.

Poster presentation - P005

Study of reactivity of germylene stabilized by boraguanidinate ligand Jiří Böserle , ibor Dostál [email protected] Department of General and Inorganic Chemistry, University of Pardubice Studentská 573, CZ-53210, Pardubice The investigation dealing with reactivity of germylene 1 (Fig. 1) containing in its structure a boraguanidinate ligand is presented. This type of dianionic N,N’-chelating ligands is derived from guanidinate ligands by a substitution a carbon atom by a boron atom and represents a relatively unexplored branch of organometallic chemistry[1].The electronic and steric properties of these ligands may be fine-tuned by the use of different substituents on the BN3 backbone[2]. Another interesting property of these ligands is dianionic character which significantly affects their reactivity[2]. Herein, we report on the synthesis of the rare example of boraguanidinate-stabilized germylene 1 and its reactivity with selected reagents. Observed results show that 1 may be a promising candidate for activation of various compounds especially small molecules.

Figure 1. Structure of studied germylene 1.

Acknowledgements: The authors thank the Grant agency of the Czech Republic project no. P207/12/0223. References: [1] Ch. Fedorchuk, M. Copsey, T. Chivers, Coord. Chem. Rev., 2007, 251, 897-924. [2] A. M. Corrente, T. Chivers, Inorg. Chem., 2008, 47, 10073-10080.

Poster presentation - P006

Reactions of a Barrelene-type Dialumane Bearing Bulky Aryl Substituents with Lewis Bases Koichi Nagata, Tomohiro Agou, Takahiro Sasamori, Norihiro Tokitoh* [email protected] Institute for Chemical Research, Kyoto University Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan Recently, we have reported the synthesis of dialumane 1 bearing barrelene-like scaffold and its dialumene-unit transfer reactions (Tbb–Al=Al–Tbb) from 1 to other arenes (naphthalene and anthracene) via [2+4] cycloaddition reaction between the dialumene and the arenes.[1] Herein, we will describe the reactions of 1 with Lewis bases, in the expectation of trapping the corresponding the dialumene. Reaction of 1 with N,N-dimethyl-4-aminopyridine (DMAP) afforded the Lewis acid-base adduct 2. In contrast the treatment of 1 with 2 equivalents of tert-butyl isocyanide gave ring expansion product 3, via the insertion of one molecule of tert-butyl isocyanide to the Al–Al bond of 1 (Scheme 1).[2] Structures and properties of the newly obtained ring system containing two Al atoms, 2 and 3 will be discussed.

Scheme 1. Reactions of barrelene-type dialumane 1 with Lewis bases.

References: [1] T. Agou, K. Nagata, N. Tokitoh, Angew. Chem. Int. Ed. 2013, 52, 10818. [2] Example of insertion reactions of isocyanides to Al–Al single bond: (a) W. Uhl, U. Schütz, Z. Anorg. Allg. Chem. 1995, 621, 823. (b) W. Uhl, U. Schütz, S. Phol, W. Saak, Z. Anorg. Allg. Chem. 1996, 622, 373. (c) W. Uhl, U. Schütz, W. Hiller, M. Heckel, Chem. Ber. 1994, 127, 1587.

Poster presentation - P007

In-Situ Activation of C-C Multiple Bonds Mediated by AmidinatoAluminium Framework Tomáš Chlupatý , Michal Bílek, Zdeňka Růžičková, Aleš Růžička [email protected] Department of General and Inorganic Chemistry, Faculty of Chemical Technology University of Pardubice, Studentská 573, CZ-532 10, Pardubice, Czech Republic The activation of electron-rich fragments, such as multiple bonds, by low-valent main group metal complexes and their subsequent chemical transformations represent one of the most-important fields in modern organic and organometallic chemistry. Modern utilizations of these complexes, however, present numerous challenges both to the electronic and steric properties of stabilizing ligands that are currently investigated. Versatile bonding modes, high electron density and potential steric shielding of amidinato ligands predetermine their main group metal complexes to be excellent candidates for these studies[1] (especially economic and environmental friendly aluminium from the point of view of modern chemistry). The synthesis, structure and reactivity of amidinato-aluminium complexes, which could be utilized as promoters of in-situ activation of usaturated C-C systems, will be discussed in this paper. Some reactivity of target diphenylethylene-bridged dinuclear aluminium amidinates toward small molecules will be also demonstrated.

Figure 1. Synthesis and reactivity of diphenylethylene-bridged dinuclear aluminium amidinate.

Acknowledgements: Authors would like to thank the Grant Agency of Czech Republic (grant nr. P207/12/0223) for financial support. References: [1] for example: (a) S. J. Bonyhady, D. Collis, G. Frenking, N. Holzmann, C. Jones, A. Stasch, Nature Chem., 2010, 2, 865-869; (b) L. Fohlmeister, S. Liu, C. Schulten, B. Moubaraki, A. Stasch, J. D. Cashion, K. S. Murray, L. Gagliardi, C. Jones, Angew. Chem. Int. Ed., 2012, 51, 8294-8298; (c) K. Junold, J. A. Baus, C. Burschka, R. Tacke, Angew. Chem. Int. Ed., 2012, 51, 7020–7023; (d) Y. Li, K. C. Mondal, J. Lubben, H. Zhu, B. Dittrich, I. Purushothaman, P. Parameswaran, H. W. Roesky, Chem. Commun., 2014, 50, 2986-2989.

Poster presentation - P008

New aluminate compounds of low nuclearity: synthesis and catalytic activity studies. M.T. Muñoz, Tomás Cuenca, Marta E.G. Mosquera* [email protected] Departamento de Química Orgánica y Química Inorgánica, University of Alcalá Ctra. Madrid-Barcelona Km. 33,600, E-28805, Alcalá de Henares (Madrid) Aluminium is a fascinating metal due to its exciting structural chemistry and remarkable activity in catalysis.[1] In particular, aluminium alkoxide or aryloxide species have shown to be very active catalysts in ROP processes of epoxides or cyclic esters.[2] In addition, aluminium heterometallic compounds are very interesting species, especially when the metals are connected by an oxygen atom, since those compounds have shown to be very active catalysts in polymerization reactions. [3] In this context, our research is centred in the preparation of new aluminium homo and heterometallic compounds active in polymerization processes.We have synthesized new aryloxide derivatives bearing functionalized aryl moieties, in those the presence of the additional functional group in the aromatic ring offered extra coordination points that provide them with new structural features.[4] The extension of those studies to highly bulky phenols has allowed us to prepare heterometallic derivatives with unusual low nuclearity (figure 1).

Figure 1. New heterobimetallic aluminium-sodium compound. References: [1] (a) A. C. Gledhill, N. E. Cosgrove, T. D. Nixon, C. A. Kilner, J. Fisher, T. P. Kee, Dalton Trans., 2010, 39, 9472; (b) M. Brasse, J. Cámpora, M. Davies, E. Teuma, P. Palma, E. Álvarez, E. Sanz, M. L. Reyes, Adv. Synth. Catal., 2007, 349, 2111. [2] (a) G. Martínez, S. Pedrosa, V. Tabernero, M. E. G. Mosquera, T. Cuenca, Organometallics, 2008, 27, 2300; (b) H. Sugimoto, C. Kawamura, M. Kuroki, T. Aida, S. Inoue, Macromolecules, 1994, 27, 2013. [3] (a) Y. Ning, H. Zhu, E. Y. X. Chen, J. Organomet. Chem. 2007, 692, 4535; (b) A. RodriguezDelgado, E. Y. X. Chen, J. Am. Chem. Soc. 2005, 127, 961. [4] (a) M. T. Muñoz, C. Urbaneja, M. Temprado, M. E. G. Mosquera, T. Cuenca, Chem. Commun. 2011, 47, 11757; (b) M. T. Muñoz, T. Cuenca, M. E. G. Mosquera, Dalton Trans. 2014, 43, 14377.

Poster presentation - P009

Aminotroponate ligand stabilized pentacoordinate aluminium (III) complexes: Synthesis and structural characterization Mahendra Kumar Sharma, Soumen Sinhababu, and Selvarajan Nagendran* [email protected] Department of Chemistry, Indian Institute of Technology Delhi Hauz Khas, New Delhi 110 016, India Through the reaction of lithium salt of 2-ibutylamino tropone [(2-ibu)AT] with AlCl3 (0.5 equiv.) in toluene stable pentacoordinate aluminium monochloride [(2i bu)AT]2AlCl 1 has been isolated in good yield as yellow solid. The reaction of compound 1 with 1 equiv. of PhLi, 2-thienyllithium and AgOTf afforded [(2i bu)AT]2AlPh 2, [(2-ibu)AT]2AlSC4H3 3 and [(2-ibu)AT]2AlOTf 4 complexes, respectively. Further, Compound 4 was reacted with 1 equiv. of dimethylaminopyridine gave pentacoordinate cationic complex [(2i i bu)AT]2Al(DMAP)(OTf) 5. A similar reaction of 2- butylamino tropone with AlMe3 (0.5 equiv.) in toluene afforded [(2-ibu)AT]2AlMe 6. Further, Compound 6 was treated with H2O (0.5 equiv.) gave, alumoxane complex {[(2-ibu)AT]2Al}2O 7 as a yellow solid. All the novel pentacoordinate aluminium compounds 1-7 have been characterized through multi-nuclear NMR spectroscopy. Further, were characterized through single crystal X-ray diffraction studies.

Figure 1. Molecular structure of pentacoordinate alumoxane complex 7.

References: [1] (a) Asay, M.; Jones, C.; Driess, M. Chem. Rev. 2011, 111, 354. (b) Nagendran, S.; Roesky, H. W. Organometallics 2008, 27, 457. [2] Cui, C.; Roesky, H. W.; Schmidt, H.-G.; Noltemeyer, M.; Hao, H.; Cimpoesu, F. Angew. Chem. Int. Ed. 2000, 39, 4272. [3] Bakthavachalam, K.; Reddy, D. N. Organometallics 2013, 32, 3174.

Poster presentation - P010

“Strained” Metal Bonding Environments in Indium(III) Dithiolates and Their Use as Lewis Acid Catalysts Timothy S. Anderson (a), Glen G. Briand (a)*, Andreas Decken (b), Courtney M. Dickie (a), Thomas I. Kostelnik (a), Heidi M. Pickard (a) and Michael P. Shaver (c) [email protected] (a) Department of Chemistry and Biochemistry, Mount Allison University, Sackville, Canada (b) Department of Chemistry, University of New Brunswick, Fredericton, Canada (c) School of Chemistry, University of Edinburgh, Edinburgh, UK There has been increasing interest in main group metals as alternatives to expensive and toxic transition and rare earth metals as catalysts for chemical transformations.[1] Notably, indium reagents are well-established Lewis acid catalysts in organic syntheses, though the majority of compounds that have been studied include simple trivalent salts such as triflates, chlorides and oxides.[2] More recently, organometallic indium alkoxide and amide compounds have been shown to be useful for the ring opening polymerization (ROP) of cyclic esters to yield biodegradable polymers.[3] We are interested in developing the potentially rich and “tunable” reaction chemistry of Lewis acidic main group organometallic complexes. Indium thiolates are attractive candidates for such studies due to the favorability of the In-S bond, which allows for the facile synthesis and hydrolytic stability of target compounds. Further, polydentate oxo- and amino-dithiolate ligands with appropriately chosen architectures may provide “strained” indium bonding environments (e.g. 1 vs 2) and reactive species. Our recent studies into the synthesis and structural characterization of 1) methyl indium dithiolates and their use as Lewis acid cataylsts for the ring opening polymerization (ROP) of cyclic esters [4] and 2) cationic indium dithiolate complexes and their suitability as water tolerant Lewis acid catalysts for organic reactions in aqueous media will be presented.

References: [1] (a) S. Kobayashi, M. Ueno, T. Kitanosono, Top. Curr. Chem. 2012, 311, 1; (b) T. Chivers, J. Konu, Comm. Inorg. Chem. 2009, 30, 131. [2] U. Schneider, S. Kobayashi, Acc. Chem. Res. 2012, 45, 1331. [3] S. Dagorne, M. Normand, E. Kirillov, J.F. Carpentier, Coord. Chem. Rev. 2013, 257, 1869. [4] L.E.N. Allan, G.G. Briand, A. Decken, J.D. Marks, M.P. Shaver and R.G. Wareham. J. Organomet. Chem., 2013,736, 55.

Poster presentation - P011

Aluminacycles Derived from the Imidazolin-2-iminato Ligand Daniel Franz, Shigeyoshi Inoue* [email protected] Institut für Chemie, Technische Universität Berlin Straße des 17. Juni 135, GER-10623, Berlin The imidazolin-2-iminato ligand possesses pronounced 2σ- and 2π- or π electrondonating character and steric fine-tuning is easily accomplished.[1] We exploit these properties for the syntheses of main group metal hydrides with applications in the field of bond activation.[2] The dimeric aluminum dihydride 1 reacts with yellow sulfur or selenide metal to afford the aluminum hydrogensulfide 2a[2b] or hydrogenselenide 2b (Figure). The tellurium compound 3 is formed upon conversion of 1 with Bu3P=Te and is marked by an Al2N2 ring decorated by a ditelluride unit. The formation of 3 contrasts the reactivity of 1 with lower chalcogenides. The remaining hydrides at the aluminum atoms in 2 and 3 allow for further functionalization at the metal centers: Hitherto unknown types of aluminum halide hydrogenchalcogenide complexes (4) are accessible via conversion of 2 with N-bromosuccinimide (NBS) or N-iodosuccinimide (NIS).

Figure 1. Syntheses of hydrogenchalcogenides 2 and 4, as well as the ditelluride 3; a: E = S, b: E = Se, X = Br or I, Dip = 2,6-diisopropylphenyl.

References: [1] X. Wu, M. Tamm, Coord. Chem. Rev. 2014, 260, 116. [2] (a) D. Franz, E. Irran, S. Inoue, Dalton Trans. 2014, 43, 4451; (b) D. Franz, S. Inoue, Chem. Eur. J. 2014, 20, 10645; (c) D. Franz, S. Inoue, Chem. Asian. J. 2014, 9, 2083; (d) D. Franz, E. Irran, S. Inoue, Angew. Chem. Int. Ed. 2014, 53, 14264.

Poster presentation - P012

NHC-stabilized Silylphosphinoalanes / -gallanes Manuel Kapitein, Carsten von Hänisch [email protected] Fachbereich Chemie, Philipps-Universität Marburg Hans-Meerwein-Straße 4, 35043 Marburg Since compounds containing elements of groups 13 and 15 have been in the focus of research, they appear mainly in form of (poly)cyclic structures. Therein, stabilization of this compounds is achieved through intramolecular Lewis acid-base bonds between the group 15 lone pair and the group 13 metal.[1,2] Herein we present new examples of this structural type, which contain bulky substituents on both, metal and phosphorus atoms. With the tBu2-functionality at the metal atom as well as the tBuPh2Si-group, the steric hindrance is nearly maximized. For many of this cyclic compounds we were able to cleave the ring with the help of N-heterocyclic carbenes and obtain monomeric NHC:M(R2)-P(H)SiR3species, which are unknown until recently (Fig.1a).[3] Besides this, structures of cyclic aluminum / gallium-phosphorus four membered rings with Lewis base stabilized metal atoms as well as free phosphorus lone pairs are displayed (Fig.1b).[4]

Figure 1. Schematic pathway to monomeric species and molecular structure of an example (a) and a Lewis acid stabilized cycle and the corresponding HOMO (b).

References: [1] R. L. Wells, Coord. Chem. Rev. 1992, 112, 273–291. [2] M. Matar, S. Schulz, U. Flörke, Zeitschrift für Anorg. und Allg. Chemie 2007, 633, 162–165. [3] M. Kapitein, C. von Hänisch, Eur. J. Inorg. Chem. 2015, 2015, 837–844. [4] M. Driess, S. Kuntz, K. Merz, H. Pritzkow, Chem. Eur. J. 1998, 4, 1628–1632.

Poster presentation - P013

Reactivity of N→Ga Coordinated Organogallium compounds T. Řičica, R. Jambor, Z. Růžičková [email protected] Department of general and inorganic chemistry University of Pardubice, Faculty of Chemical Technology, Studentská 95, 53210 Pardubice, Czech Republic The N→Ga coordinated organogallium dichlorides L1-3GaCl2[1] (1 - 3) containing either N,C,N-chelating ligands L1-2 (L1 is 2,6-(Me2NCH2)2C6H3- and L2 is {(2,6iPr2C6H3)N=CH}2C6H3-) or C,N-chelating ligand L3 (L3 = {(2-iPr2C6H3)N=CH}-4,6tBu2C6H2-) were prepared (Chart 1). The substitution reactions of 1 – 3 with Li2X (X = S, Se, Te), KC8, or LiNEt2 were further studied. The products of those reactions will be discussed.

Acknowledgements: The authors would like to thank the Grant Agency of the Czech Republic (1507091S and 15-07912S) for financial support. References: [1] Yamaguchi., Science of Synthesis., 2004, 7, 387.

Poster presentation - P014

Synthesis of Gallium Chalcogenide Clusters with Organic Functionality Katharina Hanau, Stefanie Dehnen* [email protected] Department of Chemistry, Philipps-Universität Marburg Hans-Meerwein-Str. 4, DE-35032 Marburg The synthesis of organo-functionalized germanium and tin chalcogenide clusters has been well-established over the last few years. Depending on the used elements and the organic moiety, different structural motives were obtained, and both the inorganic clusters and the organic moieties had been modified in different reactions, which resulted in compound with interesting properties.[1,2] Replacing the group 14 elements with group 13 elements, such as gallium, the formation of new compounds with different properties can be expected. For this purpose, the hydrogallation of alkynes with HGaCl2[3] is a necessary first step to link functional groups to the gallium atom. The alkenyl chloro gallanes that are obtained this way can then be reacted with chalcogenide sources to generate organo-functionalized gallium chalcogenide clusters, the structural motives of which are to be determined by single crystal x-ray diffraction analysis.

Figure 1. Synthesis of alkenyl chloro gallanes and subsequent experiment.

References: [1] (a) Z. Hassanzadeh Fard, C. Müller, T. Harmening, R. Pöttgen, S. Dehnen, Angew. Chem. 2009, 121, 4507 – 4511. (b) S. Heimann, M. Holynska, S. Dehnen, Z. Anorg. Allg. Chem. 2012, 638, 1663 – 1666. (c) J. P. Eußner, B. E. K. Barth, E. Leusmann, Z. You, N. Rinn, S. Dehnen, Chem. Eur. J. 2013, 19, 13792 – 13802. [2] (a) Z. Hassanzadeh Fard, L. Xiong, C. Müller, M. Holynska, S. Dehnen, Chem. Eur. J. 2009, 15, 6595 – 6604. (b) Z. Hassanzadeh Fard, R. Clérac, S. Dehnen, Chem. Eur. J. 2010, 16, 2050 – 2053. [3] W. Uhl, M. Claesener, Inorg. Chem. 2008, 47, 4463 – 4470.

Poster presentation - P015

Hume-Rothery Phase-inspired molecular chemistry – Synthesis of intermetalloid transition metal/group 13 clusters Jana Weßing, Chelladurai Ganesamoorthy, Christian Gemel, Roland A. Fischer* [email protected] Chair of Inorganic Chemistry II, Ruhr-University Bochum Universitätsstr. 150, 44801 Bochum, Germany In light of the growing significance of nanoalloys in material science, the investigation of their molecular congeners, that is closely-related mixed-metal clusters, has aroused interest as a means to elucidate properties of the respective parent materials. In this regard, the synthesis of Hume-Rothery Phase-derived clusters combining transition metals (TM) and group 13 elements (E) is particularly challenging. In this contribution, we will present a novel pathway towards intermetalloid TM/E clusters based on the coordination chemistry of the exotic ligand ECp* (Cp* = pentamethylcyclopentadienyl) at TM centers. The reaction of AlCp* with [(IPr)AuH] or [PPh3CuH]6 yields [Au8(AlCp*)6] and [Cu6(AlCp*)6H4], respectively, the first representatives of this new class of homoleptic ECp*-decorated TM clusters.[1] Even larger clusters are accessible, as proven by the synthesis of [Cu43(AlCp*)12] from [Cu6(AlCp*)6H4] and [Cu(Mes)]5 (Mes = mesityl). All these systems feature mixed-metal cores comprising nested polyhedra of “naked“ TM centers and ligated Al atoms, which, for [Cu6(AlCp*)6H4], are related to structural motifs of well-known Hume-Rothery Phases, such as Cu5Zn8. Additionally, [Cu6(AlCp*)6H4] reacts with benzonitrile in a hydrometallation reaction to give [Cu6(AlCp*)6(N=CHPh)H3], which may serve as a molecular equivalent of potential intermediates in hydrogenation reactions at Hume-Rothery nanophases, as reported by Armbrüster et al.

Figure 1. Molecular structures of [Cu6(AlCp*)6H4], [Cu43(AlCp*)12] and [Au8(AlCp*)6].

References: [1] C. Ganesamoorthy, J. Weßing, C. Kroll, R.W. Seidel, C. Gemel, R.A. Fischer, Angew. Chem. Int. Ed. 2014, 53, 7943.

Poster presentation - P016

The impact of silyl-groups in β-position on the electronic systems of phospholes Andreas Kirchmeier, Dieter Klintuch, Rudolf Pietschnig* [email protected] Chemische Hybridmaterialien, Institut für Chemie, Universität Kassel Heinrich-Plett-Straße 40, 34132, Kassel, Germany In the last decades the chemistry and properties of phospholes have been investigated thoroughly.[1] Because of the conjugation and tunability of their π-systems they were found to be very attractive building blocks as organic semiconductors.[2] Although a lot of phosphole derivatives were synthesized by changing the functional groups at the phosphorus atom or in α-position, the effect on the opto-electronic characteristics of substituents in β-position only recently started to emerge.[3] Therefore we present a general and flexible synthetic method for introducing functional groups in β-position of phospholes. According to our procedure we synthesized phospholes with silylgroups in the backbone (see figure 1) and investigated the resulting optical properties.

Figure 1. Structural motif of the synthesized phospholes.

References: [1] (a) F. Mathey, Chem. Rev., 1988, 88, 429-453. (b) F. Mathey, Coord. Chem. Rev., 1994, 137, 1-52. [2] (a) T. Baumgartner, R. Réau, Chem. Rev., 2006, 106, 4681-4727. (b) M. Hissler, P. W. Dyer, R. Réau, Coord. Chem. Rev., 2003, 244, 1-44. [3] O. Fadhel, Z. Benkö, M. Gras, V. Deborde, D. Joly, C. Lescop, L. Nyulászi, M. Hissler, R. Réau, Chem. Eur. J., 2010, 16, 11340-11356.

Poster presentation - P017

n and π Complexes of NHC-stabilized Disilicon(0) Marius I. Arz, Gregor Schnakenburg, Alexander C. Filippou* [email protected] Institut für Anorganische Chemie, Rheinische Friedrich-Wilhelms-Universität Bonn Gerhard-Domagk-Straße 1, GER-53121, Bonn Various silicon species in low oxidation states are important intermediates in chemical vapour deposition for the production of semiconductors and solar cells or in the Müller-Rochow process. Recent developments in molecular silicon chemistry revealed that N-heterocyclic carbenes (NHCs) are capable of stabilizing silicon centers in unusual low oxidation states. Intriguing examples are the Si(II)-halides SiX2(NHC) (X = Cl, Br, I; NHC = N-heterocyclic carbene) and SiClAr(NHC), which have been shown to be versatile building blocks in low-valent silicon chemistry.[1] In comparison, the reactivity of the zerovalent silicon compounds (NHC)Si=Si(NHC) (1)[2a] and Si(bNHC) (b(NHC) = bis(N-heterocyclic carbene))[2b] still needs to be explored. Recently, we reported on the isolobal relationship of compound 1, the phosphasilenylidene ArP=Si(NHC) and diphosphenes ArP=PAr (Ar = aryl group), bearing similar frontier orbitals with an almost isoenergetic n+ (E–E) lone pair orbital (HOMO) and π(E–E) orbital (HOMO−1).[3] Herein, we report our studies on the complexation reactions of 1 with coinage d10 metal centers (M = CuI,[4] AgI, AuI), in which both n (η1) and π (η2) coordination modes are observed.

Figure 1. Acyclic (η1) and cyclic (η2) coordination modes of compound 1.

References: [1] See for example: a) A. C. Filippou, O. Chernov, K. W. Stumpf, G. Schnakenburg, Angew. Chem. Int. Ed. 2010, 49, 6700; b) A. C. Filippou, B. Baars, O. Chernov, Y. N. Lebedev, G. Schnakenburg, Angew. Chem. Int. Ed. 2014, 53, 565; c) Y. N. Lebedev, U. Das, O. Chernov, G. Schnakenburg, A. C. Filippou, Chem. Eur. J. 2014, 20, 9280. [2] a) Y. Wang, Y. Xie, P. Wei, R. B. King, H. F. Schaefer III, P. v. R. Schleyer, G. H. Robinson, Science 2008, 321, 1069; b) Y. Xiong, S. Yao, S. Inoue, J. D. Epping, M. Driess, Angew. Chem. Int. Ed. 2013, 52, 7147. [3] D. Geiß, M. I. Arz, M. Straßmann, G. Schnakenburg, A. C. Filippou, Angew. Chem. Int. Ed. 2015, 54, 2739. [4] See also: M. Chen, Y. Wang, Y. Xie, P. Wei, R. J. Gillard, Jr., N. A. Schwartz, H. F. Schaefer III, P. v. R. Schleyer, G. H. Robinson, Chem. Eur. J. 2014, 20, 9208.

Poster presentation - P018

A H-substituted Silylium Ion Henning Großekappenberg, Katherina Rüger, Dennis Lutters and Thomas Müller* [email protected] Carl von Ossietzky University Oldenburg Institute of Chemistry Carl von Ossietzky Straße 9-11, 26129 Oldenburg, Federal Republic of Germany In the recent past a series of intramolecular stabilized silylium ions were synthesized and well investigated.[1] Intriguingly [Si-H]-substituted silylium ions have not been observed in condensed phase yet.[2] Here we present the ambitious synthesis of these highly reactive compounds (Figure).[3] The challenge is to find the right balance between sterically demanding substituents, which are necessary for kinetic stabilization, while keeping the hydride accessiblefor Bartlett–Condon–Schneider (BCS) hydride transfer reaction. Proton coupled 29Si INEPT NMR experiment is an easy way to identify the [Si‑H] functionality of such compounds (Figure).

Figure 1. Synthesis by BCS hydride transfer reaction and proton coupled silicon INEPT NMR of silylium ion 2.

References: [1] (a) S. Duttwyler, Q.-Q. Do, A. Linden, K. K. Baldridge, J. S. Siegel, Angew. Chem. 2008, 120, 1743-1746; (b) T. Müller, in Functional Molecular Silicon Compounds I, Vol. 155 (Ed.: D. Scheschkewitz), Springer International Publishing, 2014, pp. 107-162. [2] (a) I. S. Ignat’ev, T. A. Kochina, D. V. Vrazhnov, Russ. J. Gen. Chem. 2007, 77, 575-580; (b) G. Rasul, J. L. Chen, G. K. S. Prakash, G. A. Olah, J. Phys. Chem. A 2010, 114, 4394-4399; (c) D. G. Gusev, O. V. Ozerov, Chemistry – A European Journal 2011, 17, 634-640; (d) A. F. DeBlase, M. T. Scerba, T. Lectka, M. A. Johnson, Chem. Phys. Lett. 2013, 568–569, 9-13. [3] C. Gerdes, W. Saak, D. Haase, T. Müller, J. Am. Chem. Soc. 2013, 135, 10353-10361.

Poster presentation - P019

Activation of 7-Silanorbornadienes by NHCs – A Fast and Selective Way to NHC Stabilized Hydridosilylenes Dennis Lutters, Thomas Müller* [email protected] Institute of Chemistry, Carl von Ossietzky Universität Oldenburg Carl von Ossietzky Straße 9-11, 26129 Oldenburg, Federal Republic of Germany 7-Silanorbornadienes such as 1[1,2] are known to be a source of silylenes by thermolysis and photolysis.[3] A new method for the preparation of hydridosilylenes such as 3 is the activation of 7-silanorbornadienes 1 with N-heterocyclic carbenes e.g. 2. In a fast and selective reaction at room temperature NHC stabilized hydridosilylene 3 can be synthesized via the elimination of anthracene from 1. Up to now only a few examples of such species are known.[4,5] The reactivity of compound 3 towards acetylenes and metal complexes will be presented.

Figure 1. Activation of 7-silanorbornadiene 1 by NHC 2 to hydridosilylene 3.

References: [1] T. Sasamori, S. Ozaki, N. Tokitoh, Chem. Lett. 2007, 36, 588. [2] C. Gerdes, W. Saak, D. Haase, T. Müller, J. Am. Chem. Soc. 2013, 135, 10353. [3] For a recent summary, see M. Okimoto, A. Kawachi, Y. Yamamoto, J. Organomet. Chem. 2009, 694, 1419. [4] R. Rodriguez, D. Gau, Y. Contie, T. Kato, N. Saffon-Merceron, A. Baceiredo, Angew. Chem. Int. Ed. 2011, 50, 11492. [5] S. Inoue, C. Eisenhut, J. Am. Chem. Soc. 2013, 135, 18315.

Poster presentation - P021

Synthesis and Reactivity of an NHC-stabilized Silicon(I) Dimer Yuk-Chi Chan and Cheuk-Wai So* [email protected] Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences Nanyang Technological University, 637371 Singapore The chemistry of novel base-stabilized heavier group 14 element(I) dimers [LË-ËL] (E = Si, Ge, Sn and Pb; L = amidinate, guanidinate, β-diketiminate, N-functionalized aryl, P-functionalized amide, etc) has attracted much attention in the past ten years.[1] They comprise a Ë-Ë single bond and a lone pair of electrons on each E atom. Their structures resemble the singly bonded structure of the heavier alkyne analogues of composition LEEL.Their reactivities showed that they are powerful reagents for the activation of small molecules, unsaturated substrates etc. Recently, several research groups demonstrated that a variety of reactive moieties can be isolated with the aid of N-heterocyclic carbene.[2] As such, we are interested in investigating whether an Nheterocyclic carbene is capable of stabilizing group 14 element(I) dimers. In this poster, we report the synthesis of the NHC-stabilized silicon(I) dimer 2 and its reactions with various substrates will be presented.

Scheme 1. Synthesis of NHC-stabilized silicon(I) dimer 2.

Acknowledgements: This work was supported by ASTAR SERC PSF grant. References: [1] Selected articles : a) S.-P. Chia, R. Ganguly, Y. Li, C.-W. So, Organometallics 2012, 31, 64156419; b) S.-P. Chia, H.-X. Yeong, C.-W. So, Inorg. Chem. 2012, 51, 1002-1010; c) S.-P. Chia, H.-W. Xi, Y. Li, K. H. Lim, C.-W. So, Angew. Chem., Int. Ed. 2013, 52, 6298-6301. [2] Selected articles : a) Y. Wang, Y. Xie, P. Wei, R. B. King, H. F. Schaefer III, P. v. R. Schleyer and G. H. Robinson, Science, 2008, 321, 1069–1071; b) R. S. Ghadwal, H. W. Roesky, S. Merkel, J. Henn and D. Stalke, Angew. Chem., Int. Ed., 2009, 48, 5683–5686; c) A. C. Filippou, O. Chernov, B. Blom, K. W. Stumpf and G. Schnakenburg, Chem.–Eur.J., 2010, 16, 2866–2872.

Poster presentation - P022

The Silyldisilene-Cyclotrisilane Equilibrium Isabell Omlora, Max Holthausenb, Josef Wenderb, and David Scheschkewitza* [email protected] (a) Krupp-Chair of General and Inorganic Chemistry, Saarland University, Am Markt, Zeile 1, GER-66125, Saarbrücken-Dudweiler (b) Institute of Inorganic and Analytical Chemistry, Max-von-Laue-Str. 7, GER-60438 Frankfurt am Main Already in the first report on a stable cyclotrisilane (Mes6Si3; Mes = 1,3,5 trimethylphenyl) Masamune et al. disclosed the photolytic generation of disilenes from such ring systems.[1] This prompted intense investigations into synthesis and reactivity of such compounds.[2] One possible approach based on the silyldisilene 1 cyclotrisilane 2 equilibrium (Scheme 1) had been discussed theoretically early on [3], but realized experimentally only recently.[4] Treatment of a disilenide (Tip2Si=Si(Tip)Li; Tip=2,4,6-triisopropylphenyl) with an excess of chlorosilane provides access to various functionalized cyclotrisilanes. In the present contribution solid state structures of donor-acceptor complexes of possible intermediates of the silyldisilene-cyclotrisilane equilibrium will be presented.

Scheme 1: The silyldisilene 1 - cyclotrisilane 2 equilibrium.

References: [1] S. Masamune, Y. Hanzawa, S. Murakami, T. Bally, J. F. Blount, J. Am. Soc., 1982, 104, 4, 1150. [2] M. Weidenbruch, Chem. Rev., 1995,95, 1479. [3] A. Sax, Chem. Phys. Lett., 1986, 129,1, 66. [4](a) D. Scheschkewitz, K. Abersfelder, J. Am. Chem. Soc., 2008, 130, 4114; (b) D. Scheschkewitz, K. Abersfelder, A. J. P. White, H. S. Rzepa, Science,2010, 327, 564.

Poster presentation - P023

Reactivity of cyclotrisilene with multiply-bonded molecules Hui Zhao, Michael J. Cowley, Moumita Majumdar, Volker Huch, David Scheschkewitz* [email protected] Krupp-Chair of General and Inorganic Chemistry, Saarland University 66125 Saarbrücken-Dudweiler, Germany The cyclotrisilene motif as the heavier cousin of cyclopropene is particular inasmuch as that its bonding situation and hence reactivity can be expected to be governed by the considerable ring strain imposed by the three-membered ring.[1] Research reveal the cyclotrisilene shows reactivity towards less reactive unsaturated compounds. For instance, synthesis of functionalized cyclic disilenes via ring expansion of cyclotrisilenes with isocyanides was reported by Sekiguchi and Scheschkewitz.[2] In addition, carbonylation of cyclotrisilenes be achieved by employing CO.[3] Very recently, the phosphide delivery to a cyclotrisilene was also disclosed.[4] Here we report the reactivity of cyclotrisilene with molecules with carbon-carbon triple bond as well as nitrogen-nitrogen double bond. All of the reactions proceed under mild conditions. Cyclotrisilene 1 react with diphenylacetylene and 1,4-bis(ethynyl)benzene produce the 1:1 adducts 2 and 3, alternatively. In the case of azobenzene, the double bond of two nitrogen atoms is cleaved, resulting in a five-membered ring with a weak interaction between the two Si atoms which connected with two N atoms.

Figure 1. Reactions of cyclotrisilene with diphenylacetylene and 1,4-bis(ethynyl)benzene (above) and with azobenzene (below).

References: [1] Wu, W., B. Ma, J. I-Chia Wu et al. Chem. Eur. J. , 2009, 15, 9730-9736. [2] Ohmori, Y., M. Ichinohe, A. Sekiguchi et al. Organometallics, 2013, 32, 1591-1594. [3] Cowley, M. J., Y. Ohmori, V. Huch et al. Angew. Chem. Int. Ed., 2013, 52, 13247-13250. [4] Robinson, T. P., Cowley, M. J, D. Scheschkewitz et al. Angew. Chem. Int. Ed., 2014, 54, 683-686.

Poster presentation - P024

Metal-Silicon Triple Bonds: [2+2] Cycloadditions of Alkynes and Heteroalkynes Bernhard Baars, Oleg Chernov, Gregor Schnakenburg, Alexander C. Filippou* [email protected] Institut für Anorganische Chemie, Rheinische Friedrich-Wilhelms-Universität Bonn Gerhard-Domagk-Straße 1, GER-53121 Bonn Metallacyclobutadienes are key intermediates in the metathesis of alkynes, which has become an important tool in organic synthesis. Studies on heavier group 14 element homologues of this important class of organometallic compounds are very rare. First metallasilacyclobutadienes have been obtained recently upon [2+2] cycloaddition of alkynes across the metal-silicon triple bonds of molybdenum[1] and osmium[2] silylidyne complexes. Here we report on the reactions of unprecedented cationic group 6 metal silylidyne complexes[3] (1) with alkynes and heteroalkynes, and the full characterization of the resulting metallasilacyclobutadienes displaying diverse bonding modes.

Acknowledgements: We thank the Deutsche Forschungsgemeinschaft (SFB 813) for the generous financial support of this work. References: [1] O. Chernov, Novel molecular Si(II) precursors for synthesis of the first compounds with metalsilicon triple bonds (Ph.D. thesis), University of Bonn, 2012 http://hss.ulb.unibonn.de/2012/2994/2994.html. [2] a) P. G. Hayes, Z. Xu, C. Beddie, J. M. Keith, M. B. Hall, T. D. Tilley, J. Am. Chem. Soc. 2013, 135, 11780; b) Z. Xu, M. B. Hall, Inorg. Chim. Acta 2014, 422, 40. [3] A. C. Filippou, B. Baars, O. Chernov, Y. N. Lebedev, G. Schnakenburg, Angew. Chem. 2014, 126, 576; Angew. Chem. Int. Ed. 2014, 53, 565.

Poster presentation - P025

Consecutive Synthesis of Novel Cage-like Bicyclic Trisiloxanes Dominik Keiper, Michael Feierabend, Carsten von Hänisch* [email protected] Department of Chemistry, Philipps-Universität Marburg Hans-Meerwein-Straße 4, GER-35032, Marburg The bicyclic trisiloxanes we discuss on the poster are cagelike compounds, including two eight-membered ring systems. Both bridgehead atoms are connected via three O(SiMe2)2-units. These substances are considered as inorganic analogues of cryptands and also of [3.3.3]bicycloundecane, the so-called manxane.[1] Until now, some derivatives consisting of different bridgehead atoms and possible substituents are known.[2] However, there has been only one compound including silicon at this position so far.[3] Now we report the synthesis of novel bicyclic trisiloxanes of this kind with different functional groups at the bridgehead silicon atoms. The hydrolysis and condensation of the branched tetrasilane PhSi(SiMe2Cl)3 (1) with hydrochloric acid yielded the bicyclic trisiloxane Ph-Si{O(SiMe2)2}3Si-Ph (2). After protodephenylation of 2 with trifluoromethanesulfonic acid CF3SO3H (TfOH) the triflyl-substituted compound 3 was obtained. Our current work focusses on the halogenation of 3 by reaction with various halides AX (Figure 1).[4]

Figure 1. Consecutive synthesis of novel bicyclic trisiloxanes. References: [1] M. Doyle et al., Tetrahedron Lett., 1970, 42, 3619-3622. [2] (a) C. Eaborn, P. B. Hitchcock, P. D. Lickiss, J. Organomet. Chem., 1983, 252, 281-288; (b) C. von Hänisch, F. Weigend, O. Hampe, S. Stahl, Chem. Eur. J., 2009, 15, 9642-9646; (c) C. Bimbös, M. Jost, C. von Hänisch, K. Harms, Eur. J. Inorg. Chem., 2013, 4645-4653. [3] S. S. Al-Juaid, Y. Derouiche, P. B. Hitchcock, P. D. Lickiss, J. Organomet. Chem., 1988, 341, 241245. [4] (a) M. Feierabend, PhD thesis, Marburg, 2013; (b) D. Keiper, master's thesis, Marburg, 2014; (c) M. Feierabend, D. Keiper, C. von Hänisch, manuscript in preparation.

Poster presentation - P026

Metal─Silicon Multiple Bonds: Metallasilylidynes and Metallasilacumulenes Priyabrata Ghana, Gregor Schnakenburg, Alexander C. Filippou* [email protected] Institut für Anorganische Chemie, Rheinische Friedrich-Wilhelms Universität Bonn Gerhard-Domagk-Strasse 1, GER-53121 Bonn Complexes containing a multiply bonded carbon atom embedded between two transition metal centers are known since the 1980’s. Two types of these complexes have been described, the metallacumulenes (LnM=C=MLn)[1] and the metallacarbynes (L n M≡C─M n).[2] In comparison, studies on related silicon complexes have not been reported so far. This can be traced back to two intrinsic properties of silicon, which are its reluctance to form double and even more triple bonds and its anomalous low electronegativity. These properties render the isolation of metallasilacumulenes and metallasilylidynes a very challenging goal. In the present work a systematic approach to these unprecedented classes of compounds is reported taking advantage of the specific stereoelectronic properties of scorpionato ligands. The target complexes 1 and 2 have been analyzed by quantum theory, and first reactions will be reported.

Acknowledgements: We thank the Deutsche Forschungsgemeinschaft (SFB 813) for the generous financial support of this work. References: [1] V. L. Goedken, M. R. Deakin, L. A. Bottomley, J. Chem. Soc. Chem. Commun. 1982, 607. [2] S. L. Latesky, J. P. Selegue, J. Am. Chem. Soc. 1987, 109, 4731.

Poster presentation - P027

The Versatile Reactivity of an NHC-stabilized Silicon(II) Monohydride Carsten Eisenhut, Tibor Szilvási, Shigeyoshi Inoue* [email protected] Department of Chemistry, Technische Universität Berlin Straße des 17. Juni 115, GER-10623, Berlin Since the first isolation of an N‑heterocyclic silylene, a number of silylenes have been isolated by taking advantage of thermodynamic and kinetic stabilization. However, the chemistry of silylene hydrides is hardly explored due to their highly reactive nature. Silylene hydrides are of great interest because of their potential for diverse applications and can generally be isolated by utilizing a donor (Lewis base) and an acceptor (Lewis acid) stabilization. In this contribution, we report on the synthesis and reactivity of the novel acceptor-free silylene hydride 1 equipped with an Nheterocyclic carbene (NHC) as supporting ligand (Figure 1).[1] Interestingly, this NHC-stabilized silylene hydride 1 features three reactive sites (the lone pair on silicon, the Si-H bond, and the NHC). In fact, silylene 1 shows versatile reactivities towards transition metal complexes and unsaturated organic compounds. For example, the silylene-iron complex 2 was isolated from the reaction of 1 with Fe2(CO)9, whereas silylene 1 reacts with Ni(COD)2 to afford the dihydrodisilene complex 3. Moreover, the reactions of 1 with acetylenes afforded silole 4 via [2+2+1] cycloaddition and 1-alkenyl-1-alkynylsilane 5 via the C-H abstraction depending on the substrate.[2] In addition, DFT calculations suggest that NHC-supported zwitterionic transition states and intermediates play a significant role in these reaction.

Figure 1. Selected reactivities of the silylene monohydride 1.

References: [1] S. Inoue, C. Eisenhut, J. Am. Chem. Soc. 2013, 135, 18315. [2] C. Eisenhut, T. Szilvasi, N. C. Breit, S. Inoue, Chem. Eur. J. 2015, 21, 1949.

Poster presentation - P028

SYNTHESIS OF INTRAMOLECULARLY COORDINATED ORGANOSILANES M. Novák, R. Jambor [email protected] Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice Studentská 573, Pardubice 532 10, Czech Republic Organosilanes play important roles in many areas of organic syntheses. Hydrosilanes R3Si–H are useful reagents for the hydrosilylation of multiple bonds, reduction of various functional groups, preparation of a silanols R3Si–OH, etc.1 Our attempts to synthesize an N→Si intramolecularly coordinated organosilanes of general formula PhL1,2SiHR (where L1 and L2 are C,N-chelating ligands containing CH=N imine group and R is Ph or H) yielded organosilicon amides possessing silaindole structural motive in their structures (see Figure 1).2 Isolated organosilicon amides are an outcome of the spontaneous hydrosilylation of the CH=N imine moiety induced by N→Si intramolecularly coordination. This unexpected fact initiated us to extend the spontaneous hydrosilylation induced by N→Si intramolecularly coordination also to N,N-chelating ligands derived from pyridine or 1H-pyrrol and for that study we efficiently used trichlorosilane as hydrosilylation agent.

Acknowledgements: The authors would like to thank the Grant Agency of the Czech Republic (1507091S) for financial support. References: 1 a) M. A. Brook, Silicon in Organic, Organometallic, and Polymer Chemistry, Wiley, 2000, ch. 8, p. 171–188; b) P. D. Lickiss, Adv. Inorg. Chem.1995, 42, 147. 2 M. Novák, . Dostál, M. Alonso, F. De Proft, A. Růžička and R. Jambor, Chem. Eur. J., 2014, 20(9), 2542.

Poster presentation - P029

A Highly Reactive “Half-Parent” Phosphasilene and Iminosilane LSi=EH (E = N, P) Kerstin Hansen, Tibor Szilvási, Burgert Blom and Matthias Driess [email protected] Technische Universität Berlin, Department of Chemistry Strasse des 17. Juni 135, GER-10623 Berlin, Germany Double bond species with silicon and elements of the 15th group have attracted considerable attention owing to their high reactivity, which is induced by the pronounced polarity of the Siδ+-Eδ- (E = N, P) bond.[1] Herein we report the synthesis of a highly ylidic phosphasilene and iminosilane with a PH and NH moiety, respectively.[2-4] Both compounds are labile in solution and show different reactivities. The reaction of DMAP with the „half-parent“ phosphasilene affords the donorstabilized form, whereas the reaction with the iminosilane resulted in the activation of the α C-H bond of DMAP. To further elucidate the experimentally observed reactivity, DFT calculations were carried out and will be presented.

Figure 1. Above: “Half-Parent” Phosphasilene Below: “Half-Parent” Iminosilane.

References: [1] R. C. Fischer, P. P.Power, Chem. Rev. 2010, 110, 3877. [2] K. Hansen, T. Szilvási, B. Blom, S. Inoue, J.-D. Epping, M. Driess, J. Am. Chem. Soc. 2013, 135, 11795. [3] K. Hansen, T. Szilvási, B. Blom, E. Irran, M. Driess, Chem. Eur. J. 2014, 20, 1947. [4] K. Hansen, T. Szilvási, B. Blom, M. Driess, J. Am. Chem. Soc. 2014, 136, 14207.

Poster presentation - P030

Reactivity of Phosphorus-functionalized Low-valent Silicon Compounds towards Transition Metal Complexes Nora C. Breit, Shigeyoshi Inoue [email protected] Department of Chemistry, Technische Universität Berlin Straße des 17. Juni 135, GER-10623 Berlin Low-valent silicon compounds have high potentials for applications in catalysis, organic synthesis, and materials science. Silylenes with an electron lone pair on silicon and silenes marked by an element-silicon double bond are the key players in this field. The incorporation of phosphorus into these species induces polarized bonds based on their different electronegativities and gives rise to novel properties and reactivities. In spite of their intriguing prospect, the reactivity of phosphinosilylenes and phosphasilenes with transition metals is scarcely studied. We focus on the reactivity of phosphinosilylene 1 and phosphasilene 2 (Figure 1).[1] 1 and 2 are additionally featuring trimethylsilyl (TMS) groups that can shift from phosphorus to silicon and back or be completely removed.[1,2] Hence, novel pathways as observed in reactions of 2 with group 10 transition metals affording 3 and 4 are available.[3] In this presentation we give a short overview on the reactions previously described for 1 and 2 and subsequently focus on our newest results. In reactions of 1 and 2 with tungsten and iron carbonyl complexes species 5 and 6 were obtained that are suitable for in depth studies.[4]

Figure 1. Reactivity of phosphinosilylene 1 and phosphasilene 2 towards nickel, platinum, iron, and tungsten complexes.

References: [1] S. Inoue, W. Wang, C. Präsang, M. Asay, E. Irran, M. Driess, J. Am. Chem. Soc. 2011, 133, 2868. [2] N. C. Breit, T. Szilvási, S. Inoue, Chem. Eur. J. 2014, 20, 9312. [3] N. C. Breit, T. Szilvási, T. Suzuki, D. Gallego, S. Inoue, J. Am. Chem. Soc. 2013, 135, 17958. [4] N. C. Breit, T. Szilvási, S. Inoue, manuscript under preparation.

Poster presentation - P031

A Low Valent Silicon-Rhodium and -Cobalt Four-Membered Ring Sabrina Khoo, Cheuk-Wai So* [email protected] Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences Nanyang Technological University Singapore 637371 Base-stabilized heavier group 14 element(I) dimers of composition [LË-ËL] (E = Si, Ge, Sn and Pb; L = supporting ligand) have attracted much attention in the past few years due to their unique structures and reactivities.[1] They are stabilized kinetically by a variety of ligands such as amidinate, guanidinate, β-diketiminate, Nfunctionalized aryl and P-functionalized amide etc. They are powerful reagents, which resemble transition metal complexes to activate small molecules and unsaturated substrates. However, their reactivity toward transition metal complexes are underdeveloped. In this poster, we report the reaction of the amidinate-stabilized silicon(I) dimer [L1SiSiL1] (1; L1 = PhC(NtBu)2) with [Rh(cod)Cl]2 and CoBr2 to form complexes comprising Si2M2 rings (M = Rh, Co), respectively. They were characterized by NMR spectroscopy, X-ray crystallography and DFT calculations.

Figure 1. Synthesis of the Si2Rh2 ring 2.

Acknowledgements: This work is supported by AcRF Tier 1 grant References: [1] Selected articles : a) S.-P. Chia, R. Ganguly, Y. Li, C.-W. So, Organometallics 2012, 31, 64156419; b) S.-P. Chia, H.-X. Yeong, C.-W. So, Inorg. Chem. 2012, 51, 1002-1010; c) S.-P. Chia, H.-W. Xi, Y. Li, K. H. Lim, C.-W. So, Angew. Chem., Int. Ed. 2013, 52, 6298-6301.

Poster presentation - P032

Synthesis and Properties of Silicon Based Crown Ether Analogues Kirsten Reuter, Carsten von Hänisch* [email protected] Department of Chemistry, Philipps-Universität Marburg Hans-Meerwein Straße 4, GER-35043, Marburg Cyclosiloxanes are compared to organic crown ethers less attractive for the complexation of cations. This is due to the low basicity of oxygen in siloxanes and to date different explanations are discussed.[1] Intriguingly, recent studies have shown that the basicity of oxygen is increased at the presence of Si2-units, for example in the cylic silaether (Me4Si2O)2.[2] Our research is focused on disilane based crown ether analogues and their complexation potential. At the first step, one ethane unit of a crown ether has formally been substituted by disilane. Study of the alkaline metal complexes confirms the increased coordination potential of disilane based crown ethers: The bond length of silicon substituted oxygen to the metal is slightly shortened compared to the organic substituted oxygen atoms.

Figure 1. Hybrid crown ethers with one disilane unit.

Acknowledgements: We thank the Deutsche Forschungsgemeinschaft for financial support References: [1] S. Grabowsky, M. F. Hesse, C. Paulmann, P. Luger, J. Beckmann, Inorg. Chem. 2009, 48, 4384. [2] M. Cypryk, J. Kurjata, J. Chojnowski, J. Organomet. Chem. 2003, 686, 373

Poster presentation - P033

Configurationally Stable Pentaorganosilicates Leon J. P. van der Boon, J. Chris Slootweg, Koop Lammertsma and Andreas W. Ehlers* [email protected] Department of Chemistry and Pharmaceutical Sciences, VU University Amsterdam de Boelelaan 1083, 1081 HV, Amsterdam, the Netherlands Silicon is capable of forming hypercoordinate structures with more than four substituents. Usually, these structures are only found as reactive intermediates, but they can be stabilized by withdrawing electron density from the silicon centre. Most of these hypercoordinate silicon species contain nitrogen or oxygen as they bind strongly to silicon. However, it is also possible to obtain pentaorganosilicates with five carbon substituents using stabilizing bisaryl ligands (Figure 1, top).[1] Pentaorganosilicates, like most pentacoordinate species, show dynamic behavior via multiple Berry pseudorotations (Figure 1, bottom) and therefore any chiral information is lost due to permutations of the substituents.[2] We now present a full experimental and theoretical study on pentaorganosilicates 1 and 2 with substituents that inhibit the vital Berry pseudorotation making these silicates configurationally stable, thereby retaining chiral information. These concepts are also viable for pentacoordinate metal complexes, were inhibition of the Berry pseudorotation is key for a successful application in asymmetric catalysis. Therefore, coupling of catalytically active metals via the pyridine moiety in silicate 3 is also investigated.

Figure 1. Top: Various pentaorganosilicates, bottom: The Berry pseudorotation.

Acknowledgements: This work was supported by the Council for Chemical Sciences of the Netherlands Organization for Scientific Research (NWO/CW). References: [1] E.P.A. Couzijn, J.C. Slootweg, A.W. Ehlers, K. Lammertsma, Z. Anorg. Allg. Chem., 2009, 635, 1273. [2] E.P.A. Couzijn, J.C. Slootweg, A.W. Ehlers, K. Lammertsma, J. Am. Chem.. Soc., 2009, 131, 3741.

Poster presentation - P034

Functionalization and Transfer of Unsaturated Si6 Cluster Compounds Philipp Willmes, Kai Abersfelder, Volker Huch, David Scheschkewitz* [email protected] Krupp-Chair of General and Inorganic Chemistry, Saarland University Am Markt, Zeile 1, GER-66125, Saarbrücken-Dudweiler Unsaturated silicon clusters are plausible transient intermediates during the gas phase deposition of silicon materials. Cluster-like assemblies in hydrogen-rich amorphous silicon are thought to be band-gap determining.[1] The targeted syntheses of stable unsaturated silicon clusters (siliconoids) has been a challenging goal.[2] Recently, we reported that reduction of cyclotrisilane 1 yields the dismutational hexasilabenzene isomer 2[3] which can be isomerized to propellane 3, the assumed global minimum on the Si6R6 potential energy surface (Figure 1). Here we report on the functionalization of the Si6 cluster backbone and its successful transfer to a variety of different substrates.

Figure 1. Syntheses of hexasilabenzene isomer 2, propellane 3.

References: [1] Y. S. Shcherbyna, T. V. Torchynska, Thin Solid Films, 2010, 518, 204. [2] (a) D. Scheschkewitz, Angew. Chem. Int. Ed. 2005, 44, 2954; (b) G. Fischer, V. Huch, P. Mayer, S. Vasisht, M. Veith, N. Wiberg, Angew. Chem. Int. Ed., 2005, 44, 7884; (c) D. Nied, R. Köppe, W. Klopper, H. Schnöckel, F. J. Breher, J. Am. Chem. Soc., 2010,132, 10264; (d) K. Abersfelder, A. Russell, H. S. Rzepa, A. J. P. White, P. R. Haycock, D. Scheschkewitz, J. Am. Chem. Soc., 2012, 134, 16008; (e) A. Tsurusaki, C. Iizuka, K. Otsuka, K., S. Kyushin, J. Am. Chem. Soc., 2013, 135, 16340. [3] K. Abersfelder, A. J. P. White, H. S. Rzepa, D. Scheschkewitz, Science 2010, 327, 564. [4] K. Abersfelder, A. J. P. White, R. J. F. Berger, H. S. Rzepa, D. Scheschkewitz, Angew. Chem. Int. Ed. 2011, 50, 7936.

Poster presentation - P035

Synthesis and Characterization of Cyclic Acylsilanes - Precursors for Brook-Type Cyclic Silenes Michael Haas, Harald Stüger and Christa Grogger [email protected] TU Graz, Institute of Inorganic Chemistry Stremayrgasse 9, 8010 Graz, Austria Cyclic acylsilanes are versatile starting materials for the formation of previously unknown Brook-type cyclic silenes.[1] They can be synthesized in good yields (> 60 %) by a 2-step process, involving the formation of potassium silanides 2a-d from 1,1,4,4-tetrakis(trimethylsilyl)cyclohexasilane 1 and their subsequent reaction with acyl chlorides. Compounds 3a-d were isolated and characterized by X-ray data analysis, UV/Vis- spectroscopy and cyclic voltammetry.

Figure 1. Formation of Cyclic Acylsilanes

References: [1] (a) Stueger, H.; Hasken, B.; Haas, M.; Rausch, M.; Fischer, R.; Torvisco, A. Organometallics 2014, 33, 231; (b) Haas, M.; Fischer, R.; Flock, M.; Mueller, S.; Rausch, M.; Saf, R.; Torvisco, A.; Stueger, H. Organometallics 2014, 33, 5956.

Poster presentation - P036

2-(Dimethylaminomethyl)-ferrocenyl Substituted Silanols, Disilanolates and Siloxanes: Search for new Intermediates Christopher Golz, Carsten Strohmann* [email protected] Faculty of Chemistry and Chemical Biology, TU Dortmund University Otto-Hahn-Str. 6, Ger-44227, Dortmund 2-(Dimethylaminomethyl)-ferrocenyl substituted silanols represent a highly promising substance class. Due to the high steric hindrance of the ferrocene and/or the intramolecular hydrogen bonds to the amino-group, these silanols are comparatively stable in terms of condensation reactions. For the disiloxandiol, only one diastereomer was observed, in which the configuration of the silicon centers is dependent on the planar chiral ferrocenyl-substituents. The synthesis of the enantiopure compound is possible via the (Sp)‑ferrocenyllithium.[1] The cleavage of siloxanes with zinc salts or the deprotonation of silanols resulting in stable silanolates were both observed in our group.[2] Even more interesting is the hydrolysis of the methoxysilanes in the presence of zinc salts, leading to the unexpected isolation of partially hydrolyzed methoxysilanolates, granting an unique insight into the mechanism of the hydrolysis reaction of silicon compounds.

Figure 1. Disiloxandiols and silandiols derived from ferrocenyl substituted methoxysilane.

Acknowledgements: We are grateful to the Deutsche Forschungsgemeinschaft (DFG) and Fonds der Chemischen Industrie (FCI) for financial support. References: [1] P. Steffen, C. Unkelbach, M. Christmann, W. Hiller, C. Strohmann, Angew. Chem. Int. Ed. 2013, 52, 9836-9840. [2] (a) C. Däschlein, C. Strohmann, Z. Naturforsch. 2009, 64b, 1558-1566; (b) C. Däschlein, J. O. Bauer, C. Strohmann, Angew. Chem. 2009, 121, 8218-8221.

Poster presentation - P037

Synthesis and Structure of a Stable 1,2-Digermabenzene Tomohiro Sugahara, Takahiro Sasamori, Tomohiro Agou, Jing-Dong Guo, Shigeru Nagase, and Norihiro Tokitoh [email protected] Institute for Chemical Research and Fukui Institute for Fundamental Chemistry, Kyoto Univ. Gokasho, Uji, Kyoto 611-0011, Japan The replacement of carbon atoms in the benzene ring with heavier group 14 elements, generating „heavy aromatics“, has attracted many chemists as unique π conjugated ring system. However, this class of compounds is known to be highly susceptible toward the addition reaction with moisture and/or aerobic oxygen and selfoligomerization. Nowadays, many examples of the stable heavy aromatics have been synthesized by using bulky substituents with keeping their intrinsic nature of reactivity. The synthesis of stable 1,2-disilabenzenes, for example, has been accomplished by the reaction of stable disilynes with alkynes.[1] These compounds have generated great interest, especially with respect to their properties as a cyclic 6πconjugated system including a Ge=Ge moiety. Here, we will report the synthesis and isolation of the 1,2-digermabenzene via the reaction of a digermyne, TbbGeGeTbb (Tbb = 4-t-Bu-2,6-[CH(SiMe3)2]-C6H2), with two equivalents of acetylene.[2] In addition, the chemical properties, the physical properties and theoretical calculations of the obtained 1,2-digermabenzene will also be described.

References: [1] (a) R. Kinjo, M. Ichinohe, A. Sekiguchi, N. Takagi, M. Sumimoto, S. Nagase, J. Am. Chem. Soc. 2007, 129, 7766; (b) J. S. Han, T. Sasamori, Y. Mizuhata, N. Tokitoh, Dalton Trans. 2010, 39, 9238. [2] T. Sasamori, T. Sugahara, T. Agou, J. Guo, S. Nagase, R. Streubel, N. Tokitoh, Organometallics 2015, in press. [DOI: 10.1021/om501204u]

Poster presentation - P038

Sila- and Germacyclopentadienyl Radicals vs. Anions Crispin R. W. Reinhold, Thomas Müller* [email protected] Institute of Chemistry, Carl von Ossietzky University of Oldenburg Carl von Ossietzky Str. 9 - 11, 26129 Oldenburg, Federal Republic of Germany Sila- and germacyclopentadienes[1] (siloles and germoles) show remarkable electronic and photo physical properties.[2] By creating localized spin centres in those heterocycles, interesting functionalities could be added. Especially the integration of those systems into macromolecules would lead to cooperative effects.[3] Against this background we reduced 1-halogenated siloles and germoles and obtained respective radicals. Further reduction of the germole led to the expected mono anion. In the case of the silole a dimeric dianion is formed. The EPR spectra of the radicals and the molecular structures of the anions will be presented.

Figure 1. Reduction of halogenated siloles and germoles to radicals and anions.

Acknowledgements: Special thanks to Dr. Boris Tumanskii, Dr. Dmitri Bravo-Zhivotovskii and Prof. Yitzhak Apeloig. This work was supported by the Carl von Ossietzky University of Oldenburg. References: [1] J. Dubac, A. Laporterie, G. Manuel, Chem. Rev. 1990, 90, 215. [2] S. Yamaguchi, K. Tamao, J. Chem. Soc., Dalton Trans. 1998, 3693. [3] T. Nozawa, M. Nagata, M. Ichinohe, A. Sekiguchi, J. Am. Chem. Soc. 2011, 133, 5773.

Poster presentation - P039

Photochemical Reactivity of Cyclic Acylgermanes Dominik Schnalzer, Michael Haas, Ana Torvisco and Harald Stueger* [email protected] Institute of Inorganic Chemistry Institute for Inorganic Chemistry Graz University of Technology Stremayrgasse 9/V A-8010 Graz, Austria The reactivity of acylgermanes differs from that of acylsilanes due the fact that the acylgermanes do not undergo Brook-type rearrangement reactions.[1] Instead, upon irradiation, acylgermanes predominantly react via Norrish type-Ι cleavage of the germanium-carbon bond[2-4] to give complex product mixtures in the case of acyclic substrates because of extensive follow-up reactions of the initially formed germyl radicals.[5] In contrast, the newly synthesized cyclic acylgermanes 1a-c mainly afforded the Ge-Ge coupling product 2 after irradiation with λ > 300 nm light, which can be explained by the enhanced stability of the cyclic germyl radical 3. The previously unknown compound 2 was isolated and fully characterized spectroscopically and by single crystal X-ray crystallography. Further studies to enlarge the scope of this new method for the formation of Ge-Ge bonds are currently underway.

Figure 1. Irradiation of acylgermanes.

References: [1] A. G. Brook, Acc. Chem. Res., 1974, 7, 77. [2] K. Mochida, K. Ichikawa, S. Okui, Y. Sakaguchi, H. Hayashi, Chem. Lett., 1985, 1433. [3] M. B. Taraban,; V. I. Maryasova,; T.V. Leshina,; L. I. Rybin,; D. V. Gendin,; N.S. Vyazankin, J. Organomet. Chem., 1987 326,347. [4] S. Kiyooka,; M. Hamada,; H. Matsue,; M. Hamada,; R. Fujiyama, , J. Org. Chem., 1990 55, 5562. [5] A. G. Brook,; F. Abdesaken; H. Söllradl, J. Organomet. Chem., 1986, 299, 9-13.

Poster presentation - P040

Synthesis and Characterization of the first relatively stable Germenolates Michael Haas, Dominik Schnalzer, Ana Torvisco and Harald Stueger [email protected] Institute of Inorganic Chemistry, Graz University of Technology Stremayrgasse 9, 8010 Graz, Austria Enolates and silenolates are widely employed in organic as well as in inorganic chemistry.[1,2] However, the synthesis and characterization of germenolates was neglected. To the best of our knowledge only one study concerning germenolates has been published in literature by the group of Bravo-Zhivotovskii.[3] As we have reported earlier, it is possible to synthesize and characterize cyclic silenolates and react them with electrophiles.[4] Due to the fact that these cyclic silenolates exhibit increased stability in comparison to the acyclic derivatives, it was obvious to attempt the synthesis of the less stable germenolates. In this lecture we discuss the synthesis, spectroscopic characterization and molecular structures of the first cyclic germenolates 1a-c and the conversion of 1a,b to germene 2a,b.

Figure 1. Synthesized cyclic Germenolates and Germenes

Acknowledgements: NAWI-Graz shall be gratefully acknowledged for financial support References: [1] For general reviews about enolates, see e. g.: (a) D. Stolz, U. Kazmaier in The Chemistry of Metal Enolates, Part 1 (Eds.: Z. Rappoport, J. Zabicky), Wiley, Hoboken, 2009, pp. 355-411; (b) D. Seebach, Angew. Chem. 1988, 100, 1685-1715; Angew. Chem. Int. Ed. Engl. 1988, 27, 1624-1654; (c) P. Veya, C. Floriani, A. Chiessi-Villa, C. Rizzoli, Organometallics 1994, 13, 214-223. [2] For example see: (a) J. Ohshita, S. Masaoka, Y. Masaoka, H. Hasebe, M. Ishikawa, A. Tachibana, T. Yano, T. Yamabe, Organometallics 1996, 15, 3136; (b) T. Guliashvili, I. El-Syed, A. Fischer, H. Ottosson, Angew. Chem. Int. Ed. 2003, 42, 1640; (c) R. Dobrovetsky, L. Zborovsky, D. Sheberla, M. Botoshansky, D. Bravo-Zhivotovskii, Y. Apeloig, Angew. Chem. Int. Ed. 2010, 49, 4084. [3] I. S. Biltueva, D. A. Bravo-Zhivotovskii, I. D. Kalikhman, V. Yu. Vitkovskii, S. G. Shevchenko, N. S. Vyazankin, M. G. Voronkov, J. Organomet. Chem. 1989, 368, 163. [4] M. Haas, R. Fischer, M. Flock, S. Mueller, M. Rausch, S. Saf, A. Torvisco, H. Stueger, Organometallics 2014, 33, 5956.

Poster presentation - P041

Cationic Rearrangements in Polysilanes and Polygermasilanes Subtle Capture of Intermediates Lena Albers, Thomas Müller* [email protected] Institute of Chemistry, Carl von Ossietzky University Oldenburg Carl von Ossietzky Strasse 9-11, 26129 Oldenburg, Federal Republic of Germany Linear, permethylated polysilanes[1,2] and polygermasilanes[3,4] always transform in a Lewis acid catalysed Wagner-Meerwein analogue rearrangement, via methyl or trimethylsilyl shifts, into their branched isomers to obtain quaternary* silicon or germanium atoms. Our investigations on Lewis acid catalysed rearrangements in polysilanes and polygermasilanes give astonishing insights into silyl cation chemistry. We use hydrogen substituted polysilanes and polygermasilanes to define the position of the initial positively charged atom by hydride transfer reaction to investigate the reaction mechanism. Cationic intermediates of these rearrangements were captured by the formation of Si-H-Si bridges. This structural motif[5,6] is evidenced by low temperature NMR spectroscopy and quantum mechanical calculations. By this means we are able to propose reaction mechanisms of Lewis acid catalysed rearrangements of polysilanes and polygermasilanes.

Figure 1. Stabilisation of cationic intermediates by Si-H-Si bridges.

* quaternary = Si or Ge atom substituted with 4 silyl groups Acknowledgements: This work was supported by the ERA-chemistry program (DFG-Mu1440/8-1, FWF-I00669). References: [1] M. Ishikawa, J. Iyoda, H. Ikeda, K. Kotake, T. Hashimoto, M. Kumada, J. Am. Chem. Soc. 1981, 103, 4845. [2] H. Wagner, A. Wallner, J. Fischer, M. Flock, J. Baumgartner, C. Marschner, Organometallics 2007, 26, 6704‑6717. [3] H. Wagner, J. Baumgartner, T. Müller, C. Marschner, J. Am. Chem. Soc. 2009, 131, 5022. [4] S. Sharma, N. Caballero, H. Li, K. H. Pannell, Organometallics 1999, 18, 2855. [5] T. Müller, Angew. Chem. 2001, 113, 3123-3126. [6] A. Sekiguchi, Y. Murakami, N. Fukaya, Y. Kabe, Chem. Lett. 2004, 33, 530-531

Poster presentation - P042

Is Me3SiOK a Substitute for Me3COK in Schlosser’s Base Mixtures? Kathrin Louven, Stephan G. Koller, Carsten Strohmann* [email protected] Faculty of Chemistry and Chemical Biology, TU Dortmund University Otto-Hahn-Str. 6, GER-44227, Dortmund The use of Schlosser’s Base Mixtures is an elegant method for metalation reactions at low temperatures. Organolithium reagents are combined with potassiumalkoxides forming the reactive superbasic “ IC OR” species.[1,2] The main focus of the presented research lies on the identification of further Schlosser’s Base like systems. Potassiumalkoxide is substituted by potassiumsilanolate and the corresponding reactivity and selectivity is tested on deprotonations. Furthermore, aggregates formed in the Schlosser’s Base Mixtures t-BuLi/Me3COK and t-BuLi/Me3SiOK will be compared. The two aggregates of the formula [(Me3ElO)8K4Li4(THF)4] show different arrangements of the Li- and K-centers for El = C and El = Si. Further examples will be discussed.

Figure 1. Isolated aggregates of [(Me3ElO)8K4Li4(THF)4]; El = C, Si.[3]

Acknowledgements: We are grateful to the Deutsche Forschungsgemeinschaft (DFG) for financial support. References: [1] M. Schlosser, Pure & Appl. Chem 1988, 60, 1627-1634. [2] C. Unkelbach, D. F. O’Shea, C. Strohmann, Angew. Chem. Int. Ed. 2014, 53, 553-556. [3] W. Clegg, A. M. Drummond, S. T. Liddle, R. E. Mulvey, A. Robertson, Chem. Comm. 1999, 16, 1569-1570 (prepared from t-BuOLi/t-BuOK).

Poster presentation - P043

Syntheses and Reactions of Cationic 4-Phosphonio Substituted NHCs Kai Schwedtmann, Robin Schoemaker, Felix Hennersdorf, Jan J. Weigand [email protected] Department of Chemistry and Food Chemistry , University of Technology Dresden Mommsenstrasse 4, 01062 Dresden, Germany The use of N-heterocyclic carbenes (NHCs) in phosphorus chemistry has led to some remarkable discoveries with considerable impact in recent years. Only a handful of examples are known where the 4-position of certain NHCs can be selectively addressed leading to 4-phosphanyl substituted imidazolium salts or NHCs in the presence of chlorophosphanes[1,2a] or phosphaalkenes.[2b] In this context we present a new and facile concept for the synthesis of 4-phosphanyl substituted imidazolium triflates 1[OTf]. Subsequent functionalization leads to cationic 4-phosphonio substituted NHCs 3[OTf] exhibiting a Lewis acidic and a Lewis basic moiety which can be used in follow up chemistry.

Figure 1. Preparation of cationic 4-phosphonio substituted NHCs 3[OTf].

References: [1] K. Schwedtmann, M. H. Holthausen, K.-O. Feldmann, Jan J. Weigand, Angew. Chem. Int. Ed. 2013, 125, 14204. [2] a) D. Mendoza-Espinosa, B. Donnadieu, G. Bertrand, J. Am. Chem. Soc. 2010, 132, 7264; b) J. I. Bates, P. Kennepohl, D. P. Gates, Angew. Chem. Int. Ed. 2009, 48, 9844.

Poster presentation - P044

Synthesis and Reactivity of Ditopic Carbanionic N-Heterocyclic Carbene Complexes Jordan B. Waters*, Lajoy S. Tucker and Jose M. Goicoechea [email protected] Department of Chemistry, Chemistry Research Laboratory, University of Oxford 12 Mansfield Rd, Oxford, OX1 3TA, UK Since the discovery of the first isolable N-heterocyclic carbene (NHC) 24 years ago,[1] these compounds have gone from chemical curiosities to ubiquitous ligands in modern organometallic chemistry. NHCs can bond to metals through the “conventional” (C2) or “abnormal” (C ) positions.[2] Recently, Robinson reported the synthesis of the first N-heterocyclic “dicarbene” (NHDC), by deprotonation of an NHC resulting in a species capable of binding through the C2 and C4 positions simultaneously.[3] Accordingly, we have recently reviewed the known chemistry of ditopic carbanionic NHCs.[4] We have been investigating the reactivity of the lithium salt of the deprotonated IPr carbene towards E[N(SiMe3)2]2 complexes (E = Ge, Sn, Pb). Such reactions in an equimolar ratio result in the formation of novel germylene, stannylene or plumbylene species. We have also synthesised the analogous potassium salt (KIPr) and studied the reactivity towards EE[N(SiMe3)2]2 (E = Ge, Sn, Pb and Zn).[5] The products are all C4 bonded adducts i E[:CCH{[N(2,6- Pr2C6H3)]2C:}]E[N(SiMe3)2]2]− which in the case for E = Ge and Pb, will slowly rearrange to afford the bis-carbene adduct along with the homoleptic metal tris-amide (see Figure).

References: [1] Arduengo, A. J.; Harlow, R. L.; Kline, M. J. Am. Chem. Soc., 1991, 113, 361–363. [2] Aldeco-Perez, E.; Rosenthal, A. J.; Donnadieu, B.; Parameswaran, P.; Frenking, G.; Bertrand, G. Science, 2009, 326, 556–559. [3] Wang, Y.; Xie, Y.; Abraham, M. Y.; Wei, P.; Schaefer, H. F.; Schleyer, P. v. R.; Robinson, G. H. J. Am. Chem. Soc., 2010, 132, 14370–14372. [4] Waters, J. B. Goicoechea, J. M. Coord. Chem. Rev., 2014, DOI: 10.1016/j.ccr.2014.09.020 [5] Waters, J. B.; Goicoechea, J. M. Dalton Trans., 2014, 43, 14239.

Poster presentation - P045

Reactivity of heavier NHC-coordinated Vinylidene Analogues towards Anionic Nucleophiles David Nieder, Anukul Jana, Volker Huch, David Scheschkewitz* [email protected] Krupp-Chair of General and Inorganic Chemistry, Saarland University Am Markt Zeile 1, GER-66125, Saarbrücken-Dudweiler Vinylidene is the only electron precise isomer of acetylene, but so far derivatives have only been observed in cold matrices and as ligands in transition metal complexes.[1] Recently, we reported on the synthesis of the first two isolable heavier versions of vinylidene as donor-acceptor complexes with an N-heterocyclic carbene (1 and 2).[2] The two highly functionalized molecules (double bond between Si and Ge, lone pair at the GeII-center, base coordination) provide various opportunities for further manipulation, e.g. the reaction of 1 with phenylacetylene leading to a base-stabilized cyclic germylene and 2 with mesityl lithium resulting in NHC-coordinated heavier cyclopropylidenes after LiCl elimination.[2,3] These results prompted us to further investigate the behavior of silagermenylidene 2 towards other, differently sized, anionic nucleophiles. The various low valent germanium systems thus obtained will be discussed here.

Figure 1. Heavier NHC-coordinated vinylidenes 1 and 2.

References: [1] H.- Y. Liao, M.- D. Su, S.- Y Chu, Inorg. Chem., 2000, 39, 3522. [2] (a) A. Jana, V. Huch, D. Scheschkewitz, Angew. Chem., 2013, 125, 12401; (b) A. Jana, M. Majumdar, V. Huch, M. Zimmer, D. Scheschkewitz, Dalton Trans., 2014, 43, 5175. [3] (a) A. Jana, V. Huch, H. S. Rzepa, D. Scheschkewitz, Angew. Chem. Int. Ed., 2014, 54, 289; (b) A. Jana, I. Omlor, V. Huch, H. S. Rzepa, D. Scheschkewitz, Angew. Chem., 2014, 126, 10112.

Poster presentation - P046

Stability and Structure of Ferrocene based Carbene Analogues Zsolt elemen, Zoltán Benkő, Dénes Szieberth, Rudolf Pietschnig, Dietrich Gudat, László Nyulászi [email protected] Budapest University of Technology and Economics, Department of Inorganic and Analytical Chemistry Szt Gellért tér 4. H-1111 Budapest, Hungary The chemistry of stable carbenes is of current interest. While the most frequently investigated carbenes are N-heterocyclic carbenes (NHC), among them particularly imidazole-2-ylidenes (1, E 1 = E2: NR; E’: C:), recently a ferrocene based carbene 2 (E 1 = E2: NAd, E’: C:) has been reported as a stable compound (Figure 1).1 Electronic structure calculations indicated an increased singlet-triplet gap of 2 (E1 = E2: NH, E’: C:) with respect to (Me2N)2C, indicating a stabilization.2 In the present work we investigate the stability of analogues of 2 (E1: NH, PH, S, O; E’: C, Si, P+ and N+) by density functional calculations, using the isodesmic reaction (Figure 1). Comparision with the analogous NCHs, show that 2 type structures exhibit smaller, but still significant stabilization. Details of the electronic structure and the possible interaction between E2 and Fe throughout the investigated series will also be discussed.

Figure 1. Investigated systems E1: O, S, NR, PR; E2: C, Si, PR and the isodesmic reaction.

References: 1 U. Siemeling, C. Farber C. Bruhn Chem. Commun., 2009, 98–100; see also D. M. Khramov, E. L. Rosen, V. M. Lynch, C. W. Bielawski Angew. Chem. Int. Ed. 2008, 47, 2267 –2270. 2 C. Goedecke, M. Leibold, U. Siemeling, G. Frenking J. Am. Chem. Soc. 2011, 133, 3557–3569.

Poster presentation - P047

Acyclic Two-Coordinate Cationic Germylenes – Metal Element Bond Formation Arnab Rit, Simon Aldridge* [email protected] Chemistry Research Laboratory, University of Oxford Mansfield road, OX1 3TA, Oxford The chemistry of thermally stable divalent neutral germanium compounds has attracted a lot of attention in recent years.[1] In contrast to neutral compounds, :GeX2, related cationic germanium(II) species of the type [:Ge(L)X]+ are relatively rare.[2] Given recent interest in comparisons of fundamental properties between carbon and its heavier congeners, understanding the structure and reactivity of cationic germylenes might open up many interesting areas as has been seen for the corresponding carbenium ions. In addition, the presence of a cationic charge may lead to the isolation of unsaturated monomeric species (e.g. containing Ge=E multiple bonds) by discouraging the sorts of oligomerization processes seen for neutral analogues. Herein we present the synthesis of rare acyclic two-coordinate cationic germylenes by chloride abstraction from NHC-stabilized chlorogermylenes. Steric and electronic tuning of the substituents at germanium allows control of aggregation. Thus, smaller NHCs result in dimerization to give novel dicationic digermenes [X(L)Ge=GeX(L)]2+. Bulkier substituents yield monocationic germylenes which react cleanly with azido or diazo compounds under N2 release to give monomeric imido or alkylidene complexes.

Figure 1. Two-coordinate cationic germylenes and subsequent metal element bond formation. Acknowledgements: European Commission is gratefully acknowledged for a Marie Curie postdoctoral grant to A.R. References: [1] (a) O. Kühl, Coord. Chem. Rev., 2004, 248, 411; (b) Z. Rappoport, The Chemistry of Organic Germanium, tin and lead compounds; Wiley: Chichester, 2002; Vol. 2, p. 284-332. [2] (a) H. V. R. Dias, Z. Wang, J. Am. Chem. Soc., 1997, 119, 4650; (b) M. Stender, A. D. Phillips, P. P. Power, Inorg. Chem., 2001, 40, 5314.

Poster presentation - P048

Ferrocene-based Tetrylenes Jan Oetzel, Clemens Bruhn, Ulrich Siemeling* [email protected] Institute of Chemistry, University of Kassel Heinrich-Plett-Straße 40, GER-34117, Kassel Soon after the spectacular isolation of the first stable N-heterocyclic carbene (NHC) by Arduengo et al. in 1991, NHCs and related diaminocarbenes attained the status of ordinary compounds with very useful, but essentially unspectacular, chemical behavior.[1] In contrast to this widespread judgement, ferrocene-based NHCs of type 1a (Fig.) exhibit a highly unexpected reactivity, especially towards small molecules like CO or NH3.[2] We expect unusual properties for the heavier homologues of NHC 1a, too. The aim of this research is to synthesize and study ferrocene-based Nheterocyclic silylenes (1b) and also germylenes (1c), stannylenes (1d) and plumbylenes (1e; Fig.). The reaction of di-li-thi-ated 1,1’-diaminoferrocenes (2) with SiX4 (X = Br, Cl) affords NHSi precursors (3), which need to be reduced in the final step. Corresponding NHGe, NHSn or NHPb can be synthesized by reaction of 2 with [GeCl2(dioxane)], SnCl2or PbCl2 (Fig.). However, the reduction of NHSi precursors 3 (R = neopentyl, TMS) turned out to be a tough challenge, prompting us to investigate the use of a silicon(II) precursor. Gratifyingly, we found that the corresponding silylenoid of 1b can be generated by reaction of 2 with [SiCl2(nhc)][3]. The NHGe 1c (R = neopentyl, TMS) and the NHSn 1d (R = TMS) have been synthesized and fully characterized. The attempted synthesis of NHPb 1e led to a fascinating complex containing three Pb atoms.

Figure 1. NHC system 1a[2] and routes to corresponding N-heterocyclic silylenes (1b), germylenes (1c), stannylenes (1d) and plumbylenes (1e); Fc = 1,1’-ferrocenediyl.

References: [1] (a) F. E. Hahn, M. C. Jahnke, Angew. Chem. Int. Ed. 2008, 47, 3122; (b) M. N. Hopkinson, C. Richter, M. Schedler, F. Glorius, Nature 2014, 510, 485. [2] U. Siemeling, C. Färber, C. Bruhn, M. Leibold, D. Selent, W. Baumann, M. von Hopff-gar-ten, C. Goedecke, G. Frenking, Chem. Sci. 2010, 1, 697. [3] R. S. Ghadwal, H. W. Roesky, S. Merkel, J. Henn, D. Stalke, Angew. Chem. 2009, 121, 5793.

Poster presentation - P049

Cyclic distannene in reaction with terminal alkynes Jessica Edrich, Jens Henning, Lars Wesemann* [email protected] Institut für Anorganische Chemie, Universität Tübingen Auf der Morgenstelle 18, 72076 Tübingen, Germany Since the first distannene featuring a formal tin-tin double bond was characterized by Lappert and co-workers in 1976[1], the field of multiple bonding between heavier group 14 elements attracted great attention. Herein, we present the cyclic distannene 1 (Figure 1) in which the two tin atoms are linked to a 9,9-dimethylxanthene backbone and are sterically protected by two bulky m-terphenyl moieties (ArMes = C6H3-2,6Mes2, Mes = C6H2-2,4,6-Me3)[2]. These m-terphenyl ligands were introduced by Power and co-workers into low-valent main group element chemistry[3,4]. Increasing the steric demand on the m-terphenyl substituents yields compound 2 (ArTrip = C6H32,6-Trip2, Trip = C6H2-2,4,6-i-Pr3)[5]. Compound 2 shows no tin-tin interaction in the solid state, the backbone is planar and not folded to facilitate a shorter tin-tin distance like in case of distannene 1. Hence, 2 can be categorized as bis(stannylene). To compare their reactivity, they were reacted with terminal alkynes. The reaction of 1 and 2 with phenylacetylene yield the 1,2-distannacyclobut-3-enes 3 and 4. While the reaction of 1 to 3 is irreversible, the reaction of 2 to 4 shows reversibility at room temperature.

Figure 1. Reaction of distannene 1 and bis(stannylene) 2 with phenylacetylene.

References: [1] P. J. Davidson, D. H. Harris, M. F. Lappert, J. Chem. Soc. Dalton Trans. 1976, 2268–2274. [2] J. Henning, L. Wesemann, Angew. Chem. Int. Ed. 2012, 51, 12869–12873. [3] K. Ruhlandt-Senge, J. J. Ellison, R. J. Wehmschulte, F. Pauer, P. P. Power, J. Am. Chem. Soc. 1993, 115, 11353–11357. [4] L. Pu, A. D. Phillips, A. F. Richards, M. Stender, R. S. Simons, M. M. Olmstead, P. P. Power, J. Am. Chem. Soc. 2003, 125, 11626–11636. [5] J. Henning, K. Eichele, R. F. Fink, L. Wesemann, Organometallics 2014, 33, 3904–3918.

Poster presentation - P050

Reductive Cleavage of the CO Triple Bond by an Anionic Lowvalent Maingroup Species Cem B. Yildiz, Moumita Majumdar, Isabell Omlor, Akin Azizoglu, Volker Huch, David Scheschkewitz* [email protected] Krupp-Chair of General and Inorganic Chemistry, Saarland University 66125 Saarbrücken-Dudweiler, Germany The reduction of carbon monoxide is of considerable interest in the context of C1 chemical feedstocks of non-fossil origin[1]. The Fischer-Tropsch process for the production of hydrocarbons from CO requires transition metals as heterogeneous catalyst. In addition, numerous studies employ homogeneous transition metal complexes to achieve complete cleavage of the CO triple bond[2]. Recently, a few maingroup systems have been shown to activate carbon monoxide stoichiometrically[3]. For instance, the direct carbonylation of cyclotrisilenes without cleavage of the C≡O bond was reported by Sekiguchi and Scheschkewitz [4]. Here we report complete reductive cleavage of the triple bond in carbon monoxide by a lithium disilenide under milder conditions. The product with a cyclic Si2O2 motif at the center is isolated in almost quantitative yield. The mechanism of this seemingly complex reaction is addressed on the basis of DFT computations as well as experimentally by preparative studies involving Group 6 metal carbonyls.

Figure 1. Room temperature reductive coupling of CO by lithium disilenide.

References: [1] (a) V. Macho, M. Kralik, L. Komora, Pet. Coal, 1997, 39, 6. (b) P. M. Maitlis, J. Organomet. Chem. 2004, 689, 4366 (c) N. M. West, A. J. M. Miller, J. A. Labinger, J. E. Bercaw, Coord. Chem. Rev. 2011, 255, 881. (d) C. J. Cramer, J. Chem. Soc. Perkin Trans., 1998, 2, 1007. [2] C. Alessandro, E. Solari, R. Scopelliti, C. Floriani, J. Am. Chem. Soc. 2000, 122, 538. [3] (a) H. Braunschweig, T. Dellermann, R. D. Dewhurst, W. C. Ewing, K. Hammond, J. O. C. Jimenez-Halla, T. Kramer, I. Krummenacher, J. Mies, A. K. Phukan, A. Vargas, Nat. Chem. 2013, 5, 1025. (b) X. Wang, Z. Zhu, Y. Peng, H. Lei, J. C. Fettinger, P. P. Power, J. Am. Chem. Soc.2009, 131, 6912. [4] (a) M. J. Cowley, Y. Ohmori, V. Huch, M. Ichinohe, A. Sekiguchi, D. Scheschkewitz, Angew. Chem. 2013, 125, 13489; Angew. Chem. Int. Ed. 2013, 52, 13247. (b) M. J. Cowley, V. Huch, D. Scheschkewitz, Chem. Eur. J. 2014, 20, 9221.

Poster presentation - P051

A Computational Chemistry Quest for Viable and Stable Tin(0) Compounds, The Stannylones. Jan Turek,(a) Aleš Růžička,(b) Frank De Proft(a) [email protected] Research Group of General Chemistry (ALGC), Member of the QCMM VUB-UGent Alliance Research Group, Vrije Universiteit Brussel (VUB), Pleinlaan 2, 1050 Brussels, Belgium (b)Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Patrdubice The chemistry of heavier low-valent Group 14 elements has recently attracted considerable attention in the field of main group metal chemistry. This research has not only produced various interesting compounds,[1] but has also made it possible to demonstrate that some of these low-valent Group 14 derivatives can activate small molecules under mild conditions and display promising catalytic properties for future applications.[2] Among the low-valent Group 14 derivatives, monoatomic zero oxidation state complexes are perhaps the most fascinating.[3] The main objective of the presented work is the theoretical investigation of the structure, bonding and reactivity of a series of new unprecedented compounds where the Sn atom is present with a formal oxidation state of 0. Particular attention is focused on the stabilization effect of the hybrid N-heterocyclic carbene (NHC) ligands containing both donor and acceptor substituents (Figure 1).

Figure 1. Selected structural types of studied NHC-Sn(0) complexes.

Acknowledgements: The authors would like to acknowledge the generous financial support of FWO, under the scheme FWO Pegasus Marie Curie fellowship. References: [1] (a) Y. Mizuhata, T. Sasamori, N. Tokitoh, Chem. Rev., 2009, 109, 3479; (b) Y. Wang, G. H. Robinson, Chem. Commun., 2009, 5201; (c) C. Jones, Coord. Chem. Rev., 2010, 254, 1273; (d) P. P. Power, Acc. Chem. Res., 2011, 44, 627; (d) M. Asay, C. Jones, M. Driess, Chem. Rev., 2011, 111, 354. [2] P. P. Power, Nature, 2010, 463, 171. [3] N. Takagi, T. Shimizu, G. Frenking, Chem. Eur. J., 2009, 15, 8593.

Poster presentation - P052

Functional Binary and Ternary Organotin Selenide Clusters Niklas Rinn, Stefanie Dehnen* [email protected] Department of Chemistry, Philipps University Marburg Hans Meerwein Straße, GER-35039, Marburg Organofunctionalized tin chalcogenide clusters have shown a multitude of extraordinary properties, sparking the interest of the chemical community.[1−3] Discreet functionalized Sn/Se Cluster could be synthesized in our group by condensing R1SnCl3 (A, R1 = CMe2CH2C(O)Me) with Se(SiMe3)2 (B), leading to [(SnR1)3Se4Cl] (1) or [(SnR1)4Se6] (2) depending on the solvent and A/B ratio.[4] By adding transition metal salts M(PPh3)xCly (M = Cu, Ag, Pd) to 1 and 2 with additional equivalents of B, the inorganic core rearranges and incorporates M to form novel ternary Sn/Se/M clusters [{(R1SnIV)2Se2}3{Cu(PPh3)}2{Cu2SnII}(µ3-Se)6] (3), [(SnR1)4(SnCl)2(CuPPh3)2Se10] (4) [(R1Sn)2Se2(CuPPh3)2Se2] (5) and 1 [{(Se@Ag6)}@Ag8(µ-Se)12{(R Sn)2Se2}6] (6). When adding hydrazine hydrate to the clusters or during cluster formation further compounds 2 2 [Pd(PPh3)2Pd(PPh3)ClSn(R Cl2)Se2] (7, R = CMe2CH2C(NNH2)Me), 2 IV [Se2Pd(PPh3)2Pd(PPh3)SeH][SnCl3] (8) and [{(R Sn )2Se2}2{Cu(PPh3)}2{SnII}(µ3Se)4(µ-Se)2] (9).

Figure 1. molecular structures of 3, 6 and 7 (from left to right).

References: [1] M. Bouška, . Dostál, Z. Padělková, A. yčka, S. Herres-Pawlis, K. Jurkschat, R. Jambor, Angew. Chem. 2012, 124, 3 3 −3 0. [2] J. P. Eußner, B. E. K. Barth, E. Leusmann, Z. You, N. Rinn, S. Dehnen, Chem. Eur. J. 2013, 19, 13792−13 02

Poster presentation - P053

Group 14 element pyramidanes: theoretical studies Olga A. Gapurenko,1* Vladimir Ya. Lee,2 Ruslan M. Minyaev,1 Vladimir I. Minkin,1 Yuki Ito,2 Takahiko Meguro,2 Haruka Sugasawa,2 Akira Sekiguchi2 [email protected] (1) Institute of Physical and Organic Chemistry, Southern Federal University; (2) Department of Chemistry, University of Tsukuba (1) Stachki ave. 194/2, Rostov on Don 344090, Russian Federation; (2) Tsukuba, Ibaraki 305-8571, Japan Pyramidanes represent a group of the fundamental non-classical cage compounds. All-carbon pyramidane 1 (E = E' = C) is well-known theoretically but not yet synthesized. First heavy group 14 element pyramidanes 1 (E = C, E' = Ge, Sn; E = E' = Ge) are experimentally realized and characterized very recently.[1] We present DFT calculation of a full series of all group 14 element pyramidanes with different substituents R (Figure 1). All pyramidanes with E = C, independently of R, are stable [energy minima on potential energy surface (PES)]. Stability of heavy pyramidanes 1 (E = Si, Ge) is dictated by the size of R: from a third-order saddle point (R = H) to a local minimum or a transition state (R = SiMetBu2) on PES. This fact, as well as steric stabilization, is explained by electron density donation from R to pyramidal E‒E' bonds that can be seen by the electron localization function analysis: basin population of E‒E' bonds increases with growing R.

Figure 1. Group 14 element pyramidanes.

Acknowledgements: This work was supported by the Russian Foundation for Basic Research (14-0392101), Russian Scientific Schools (NSh-274.2014.3), and by the Japanese Society for the Promotion of Science (24550038). References: [[1](a) V. Ya. Lee, Y. Ito, A. Sekiguchi, H. Gornitzka, O. A. Gapurenko, V. I. Minkin, R. M. Minyaev, J. Am. Chem. Soc., 2013, 135, 8794; (b) V. Ya. Lee, Y. Ito, O. A. Gapurenko, A. Sekiguchi, V. I. Minkin, R. M. Minyaev, H. Gornitzka, Angew. Chem. Int. Ed., 2015, 54, in press [DOI: 10.1002/anie.201500731].

Poster presentation - P054

Quantitative Understanding of Multimetallic Cluster Growth Stefan Mitzinger*,(a) Lies Broekaert,(a,b) Werner Massa,(a) Jan Weigend,(b) Stefanie Dehnen (a) [email protected] (a) Department of Chemistry and Scientific Centre for Material Science, Philipps University of Marburg, Hans-Meerwein-Straße, D-35043 Marburg, Germany (b) Institute of Nanotechnology, Karlsruhe Institute of Technology, Hermann-vonHelmholtz Platz 1, D-76344 Eggenstein-Leopoldshafen, Germany. The chemistry of homoatomic and binary intermetalloid Zintl anions has been investigated for several decades.1 In most cases, the structural features of Zintl anions can be explained with Wade-Mingos rules or the Zintl-Klemm concept.2 By extraction of quaternary metallic phases containing K/Ge/As/MV (MV = V, Nb, Ta) with ethylenediamine (en), a new class of multimetallic Zintl anions was synthesized under encapsulation of electron-poor transition metals.3 In case of the extraction of a K/Ge/As/Ta phase five new compounds were fully characterized within one reaction allowing the elucidation of the stepwise formation of multimetallic clusters, based on the crystal structures and complementary quantum chemical studies of the involved clusters (Ge2As2)2–, (Ge7As2)2–, [Ta@Ge6As4]3–, [Ta@Ge8As4]3–, and [Ta@Ge8As6]3–. The results can even be generalized for an entire family of multimetallic clusters.

Acknowledgements: We thank the Friedrich-Ebert-Stiftung for their continuing support of this PhD project. References: [1] S. Scharfe, F. Kraus, S. Stegmaier, A. Schier, T. F. Fässler, Angew. Chem. Int. Ed. 2011, 50, 3630– 3670. [2] W. Klemm, in Festkörperprobleme 3 (Ed.: F. Sauter), Springer, Heidelberg, 1964, pp. 233–251.; K. Wade, Advances in Inorganic Chemistry and Radiochemistry 1976, 18, 1–66. [3] S. Mitzinger, L. Broeckaert, W. Massa, F. Weigend, S. Dehnen, Chem. Commun. 2015, 51, 3866– 3869.

Poster presentation - P055

CHEMISTRY OF INTRAMOLECULARLY COORDINATED STANNYLENES R. Jambor*, M. Novák [email protected] Department of General and Inorganic Chemistry UNIVERSITY of PARDUBICE, Faculty of Chemical Technology, Studentská 95, Pardubice, CZ-53210 A valuable method for increasing the understanding of intramolecular binding forces is the investigations of heavy carbene analogues (R2E), their transition metal complexes (LnM=ER2) and compounds that contain multiple bonds between heavier main group elements (R2E=ER2, RE=ER, and L n M=ER where E = group 14 elements Si, Ge, Sn and Pb). As part of a comprehensive study on intramolecularly coordinated heteroleptic organostannylenes RSnCl, we discuss here the synthesis of their transition metal complexes as well as the synthesis of the organotin(I) species (Chart 1). [1] The reactivity of mentioned compounds will be also presented.

chart 1

Acknowledgements: The authors would like to thank the Grant Agency of the Czech Republic (1507091S) for financial support. References: [1] Jambor, R.; Kasná, B.; Kirschner, K.N.; Schuermann, M.; Jurkschat, K. Angew. Chem. Int. Ed. 2008, 47, 1650.

Poster presentation - P056

Stereoselective approaches towards bisphosphano substituted tetrylenes via [3]-ferrocenophanes Denis Kargin, Rudolf Pietschnig* [email protected] Department of Chemistry, University of Kassel Heinrich-Plett-Straße 40, Germany-34132, Kassel Phosphorus bridged [n]-ferrocenophanes (n = 1, 2, 3; with n specifying the number of covalently bound atoms tethering two cyclopentadienyl rings of ferrocene) are attractive molecules for various purposes such as asymmetric catalysis[1] or metal containing polymers[2]. The discovery of reactive, transient, low-valent silicon compounds occurred almost half a century ago, but isolation of more stable Si(II) derivatives in 1986 by Jutzi[3] and especially the N-heterocyclic derivative in 1994 by West and Denk[4] attracted more attention to this interesting field. Subsequently this lead to further research on new silylenes/silylenoids for reaction with small molecules or for catalysis. Starting from the air and moisture stable compound I (R=tBu) containing trivalent chiral phosphorus atoms, we obtained suitable precursors for reduction processes or dehydrohalogenation II, exhibiting defined stereochemistry. Currently we are aiming for free phosphorus substituted tetrylenes III incorporating silicon, tin and germanium atoms linking two phosphorus atoms.

Figure 1. Phosphorus substituted ferrocene and ferrocenophane derivatives.

Acknowledgements: The authors would like to acknowledge financial support by the Deutsche Forschungsgemeinschaft (PI 353/9-1). References: [1] R.Sebesta et al., Tetrahedron: Asymmetr. 2006, 17, 2531. [2] I. Manners, D. Herberg, U.Mayer, Angew. Chem. Int. Ed. 2007, 46, 5060. [3] P. Jutzi et al., Angew. Chem. 1986, 98, 163. [4] M. Denk, R. West et al, J. Am. Chem. Soc. 1994, 116 , 2691.

Poster presentation - P057

Formation and Functionalization of Intermetalloid Clusters Lies Broeckaert (a,b), Florian Weigend, Stefan Mitzinger (1), Robert Wilson, Stefanie Dehnen* [email protected] (a) Philipps-Universität Marburg, Fachbereich Chemie and Wissenschaftliches Zentrum für Materialwissenschaften (WZMW), Hans-Meerwein-Straße, D-35043 Marburg. (b) Institut für Physikalische Chemie , Karlsruher Institut für Technologie (KIT) The formation mechanism of intermetalloid clusters is still widely unexplored. In this work we try to understand the formation processes, by combining new quantum chemical (DFT) methods and experimental studies (inorganic synthesis, characterization). The investigations are started from known precursor molecules, but also include new, unknown cluster structures (reactive intermediates) to make suggestions for the stepwise formation of two new 12- and 14-atom (Ge/As) cages, including a tantalum atom, [Ta@Ge8As4]3– and [Ta@Ge8As6]3– (cf. Figure). We make use of aninorganic retro-synthetic approach.[1] Next, the chemical reactivity of group 14/15 (Ge/As, Sn/Bi, Pb/Bi) clusters is investigated. Quantum chemical calculations are performed to study the functionalization with different organic ligands. DFT calculations help to rationalize the synthesis and choose the most promising ligands.

Figure 1. Structures and composition of the 12-atomic [Ta@GeAs](left) and the 14-atomic [Ta@GeAs]cage (right), embedding Ta.[1a] Ge atoms are colored in yellow and As in blue.

Acknowledgements: This work was supported by the Alexander von Humboldt Stiftung. References: [1] (a) S. Mitzinger, L. Broeckaert, W. Massa, F. Weigend, S. Dehnen, Chem. Comm. 2015, 51, 3866; (b) S. Mitzinger, L. Broeckaert, W. Massa, F. Weigend, S. Dehnen, 2015, submitted.

Poster presentation - P058

Reactivity of M/14/15 Intermetalloid Clusters Toward Organic and Main Group Organometallic Compounds Robert Wilson, Stefanie Dehnen* [email protected] Fachbereich Chemie, Philipps-Universität Marburg Hans-Meerwein-Straße, D-35032, Marburg Our group has reported that the binary tetrahedral 14/15 Zintl ions, [Tt2Bi2]2- (Tt = Sn, Pb), react with transition metal and lanthanide complexes in ethylenediamine to afford ternary M/14/15 intermetalloid clusters.[1] The geometric and electronic structures of these unique clusters have been thoroughly analyzed; however, study of their chemistry is inhibited by poor solubility in (or interaction with) organic non-polar or polar aprotic solvents. It is known that 9-atom group 14 Zintl ions ([Ge9]4-, [Sn9]4-, and [Ge9-xSnx]4-) may be functionalized with alkyl, alkenyl, and main group organometallic moieties, and that addition of external ligands to these compounds can have a dramatic effect on their reactivity and solubility.[2] With this in mind we have undertaken a study of the reactivity of [Tt2Bi2]2-, and its derivative intermetalloid clusters, toward organic and main group organometallic compounds (Figure 1). The ability of these clusters to undergo functionalization, cation exchange, and their behavior in alternative solvent systems will be evaluated. Preliminary results of this study are presented herein.

Figure 1. Examples of 14/15 and M/14/15 clusters, [Sn2Bi2]2- and [Pd3@Sn8Bi6]4-, and potential main group reactants.

References: [1] (a) F. Lips, R. Clerac, S. Dehnen, Angew. Chem. Int. Ed. 2011, 50, 960-964; (b) F. Lips, R. Clerac, S. Dehnen, J. Am. Chem. Soc. 2011, 133, 14168-14171; (c) F. Lips, S. Dehnen, Angew. Chem. Int. Ed. 2011, 50, 955-959; (d) R. Ababei, J. Heine, M. Holynska, G. Thiele, B. Weinert, X. Xie, F. Weigend, S. Dehnen, Chem. Commun. 2012, 48, 11295-11297; (e) R. Ababei, W. Massa, B. Weinert, P. Pollak, . ie, R. Clérac , F. Weigend, S. Dehnen, Chem. Eur. J. 2015, 21, 386-394. [2] (a) M. W. Hull, S. C. Sevov, Inorg. Chem. 2007, 46, 10953-10955; (b) F. Li, S. C. Sevov, J. Am. Chem. Soc. 2014, 136, 12056-12063.

Poster presentation - P059

An Efficient Approach to Ternary Intermetalloid Clusters and Novel Zintl Ions Bastian Weinert, Prof. Dr. Stefanie Dehnen* [email protected] Fachbereich Chemie der Philipps-Universität Marburg Hans-Meerwein-Straße D-35043 Marburg In the past, we exclusively used binary Zintl anions with a combination of Group 14/15 elements as well-soluble precursors, namely [Sn2Sb2]2− and [Sn2Bi2]2−. This has led to the generation of a large variety of ternary anions such as [Pd3@Sn8Bi6]4–, [Ln@Sn7Bi7] − and [Ln@Sn4Bi9] − (Ln = La, Ce).[1,2] Our current investigations again extent this field by transferring our approach to the Group 13/15 element combination [GaBi3]2− and [InBi3]2−.[3] Here, we present first results of this variation that indicate the subtle influence of charges, atomic radii and Lewis basicities of the involved elements. Interestingly with Ln = La, Ce, Nd, we also obtained clusters with novel structures or different charges, {[Ln@In2Bi11](µ-Bi)2[Ln@In2Bi11]} −,[4] [Sm@HGa2Bi11]x3−/[Sm@H3Ga3Bi10]1-x3−.[5] Besides characterization of the compounds, our studies include formation mechanisms and electronic structures of the uncommon intermetalloid cages.

Figure 1. Reaction scheme with resulting intermetalloid clusters and Zintl anions. Acknowledgements: This work was supported by the Deutsche Forschungsgemeinschaft (DFG, GRK 1782) and the Fonds der Chemischen Industrie (FCI, Chemie-Fonds-Stipendium for Bastian Weinert) References: [1] F. Lips, R. Clérac, S. Dehnen, J. Am. Chem. Soc. 2011, 133, 14168. [2] F. ips, M. Hołyńska, R. Clerac, U. inne, I. Schellenberg, R. Pöttgen, F.Weigend, S. Dehnen, J. Am. Chem. Soc. 2012, 134, 1181. [3] L. Xu, S. C. Sevov, Inorg. Chem. 2000, 39, 5383. [4] B. Weinert, F. Weigend, S. Dehnen,* Chem. Eur. J. 2012, 18, 13589. [5] B. Weinert, F. Müller, K. Harms, S. Dehnen,* Angew. Chem. Int. Ed. 2014, 53, 11979.

Poster presentation - P060

Subsequent chemistry of the Ge9 Zintl anion Dr. O. Kysliak, Prof. Dr. A. Schnepf* [email protected] Institute of Inorganic Chemistry, University of Tübingen Auf der Morgenstelle 18, GER-72076, Tübingen The chemistry of polyhedral Ge9 compounds is of the great interest for cluster and material chemists. It became especially fruitful during last years [1]. The first silylsubstituted metalloid cluster Ge9R3- (R = -Si(SiMe3)3) was obtained via a cocondensation route as reported by Schnepf in 2003[2]. Since in 2012 Sevov et al. published a more straightforward synthesis of this compound from K4Ge9 and RCl [3], direct modifications of Ge9clusters during substitution reaction with different R’ became possible. Here we report on the synthesis of a cluster anion with a modified silyl ligand [Ge9RPh3]- (RPh = -Si(SiMe3)2(SiPh3)) together with first subsequent reaction of this compound leading to HgGe18RPh6. Additionally, further investigations on the reaction procedure led to discovery of coordinately unsaturated metalloid cluster anion Ge9R22-, which opens the possibility to synthesize a differently substituted germanium core for the first time.

References: [1] S. Scharfe, F. Kraus, S. Stegmaier, A. Schier and Th.F. Fässler, Angew. Chem. Int. Ed., 2011, 50, 3630. [2] A. Schnepf, Angew. Chem. Int. Ed., 2003, 42, 2624. [3] F. Li, S.C. Sevov, Inorg. Chem., 2012, 51, 2706.

Poster presentation - P061

Synthesis and Reactivity of Novel Amino(imino)metallylenes Tatsumi Ochiai, Shigeyoshi Inoue [email protected] Technische Universität Berlin, Institute of Chemistry Straße des 17. Juni 135, 10623 Berlin The imidazolin-2-iminato ligand may act as a 2σ- and either a 2π- or a π-electron donor and the properties of transition-metal complexes of this ligand have been investigated thoroughly by Tamm and co-workers.[1] Recently, our group has described an silicon(II) compound stabilized by the imidazolin-2-iminato ligand.[2] However, research on Group 14 compounds comprising this ligand system has been neglected in recent years. Herein, we describe the synthesis and reactivity of novel amino(imino)stannylene 1a and germylene 1b.[3] The novel amino(imino)metallylenes 1a, b were prepared by conversion of HNIPr (NIPr = bis(2,6-diisopropylphenyl)imidazolin-2-imino) with one equiv of Lappert’s reagent (E[N(SiMe3)2]2, E = Sn, Ge). The reactions of 1a, b with B(C6F5)3 furnishes the borate salts 2a, b, respectively, though methyl-abstraction and ring-closing reaction. Treatment of 1a with DMAP (para-dimethylaminopyridine) yields its Lewis base adduct 3a and the reaction of 1b with Fe2(CO)9 affords iron carbonyl complex 4b. Furthermore, the reaction of 1a with one equiv of trimethylsilyl azide results in replacement of the amino group at the tin center by an N3substituent with concomitant elimination of N(SiMe3)3, to afford dimeric [N3SnNIPr]2 5a.

Figure 1. Reactivity of amino(imino)metallylenes.

References: [1] X. Wu, M. Tamm, Coord. Chem. Rev. 2014, 260, 116. [2] S. Inoue, . eszczyńska, Angew. Chem. Int. Ed. 2012, 51, 8589. [3] T. Ochiai, D. Franz, E. Irran, S. Inoue, Chem. Eur. J. 2015, DOI: 10.1002/chem.201500607.

Poster presentation - P062

Bis(amido)phosphanes and their use as ligands for 14th group metals Jan Vrana*, Zdenka Ruzickova, Libor Dostal [email protected] Department of General and Inorganic Chemistry, University of Pardubice Studentska 95, CZE-53210, Pardubice Boramidinates[1] and amidinates[2] were used as suitable ligands for both transition and main group metals. Analogical compounds, bis(amido)phosphanes, were also proven to be as useful ligands in organometallic and coordination chemistry[3], but their chemistry was studied in significantly lower extent. Bis(amido)phosphanes may have a wide range of bonding properties, since they can act as both monoanionic and dianionic[4] ligands, where the ligand is bonded by either covalent or coordination bond to the central atom. Novel germanium(II) and tin(II) bis(organoamido)phosphanes (for example see Figure 1) were prepared. Characterization of lithium and potassium precursors is also included.

Figure 1. Molecular structure of prepared Germanium(II) compound, hydrogen atom were omitted for clarity.

Acknowledgements: The authors thank the Grant agency of the Czech Republic project no. P207/11/0223. References: [1] C. Fedorchuk, M. Copsey and T. Chivers, Coord. Chem. Rev., 2007, 251, 897. [2] (a) F. Edelmann, Adv. Organomet. Chem. 2008, 57, 183; (b) M. Asay, C. Jones and M. Driess; Chem. Rev. 2011, 111, 354. [3] B. Eichhorn, H. Noth, T. Seifert, Eur. J. Inorg. Chem., 1999, 21, 2355. [4] M. C. Copsey, T. Chivers, Dalton Trans., 2006, 4114.

Poster presentation - P063

η3-Allyl Coordination at Tin(II) – Reactivity towards Triplebonds Kilian M. Krebs, Jessica Wiederkehr and Lars Wesemann* [email protected] Institut für Anorganische Chemie, Universität Tübingen Auf der Morgenstelle 18, 72076 Tübingen (Germany) Organotin(IV) allyl species have been known for several decades and are well established reagents in organic allylation reactions.[1] However, η3-allylic coordination towards tin is rare. In 2010, Power et al. reported the binding of a terphenyl substituted tin(II) fragment in η3-fashion towards a cyclooctatetraene dianion.[2] By switching the oxidation state to SnII in allyl tin compounds we expected new reactivity and coordination modes since unoccupied binding sites will then be available at the tin atom. Here we present a Sn II allyl complex, synthesized by reaction of Power’s triisopropyl substituted terphenyl tin(II) chloride[3] with (C3H5)MgCl, featuring an η3 coordination mode in the solid state and an uncommon 119 Sn NMR chemical shift.[4] Reaction of the tin allyl compound with an excess of alkyne or benzonitrile leads to the formation of cyclic compounds as main products (Figure 1). The alkyne induced formation of a tricyclic core goes along with dimerization of two tin allyl moieties, formation of a new C-C bond and oxidation of SnII to SnIV. Reaction with benzonitrile results in a 16 membered ring system by cleavage of the tin allyl bonds, C-H activation/hydrogen migration and dimerization of two stannylene units.

Figure 1. η3-allyl SnII complex in reaction with alkynes or benzonitrile. Trip = 2,4,6triisopropylphenyl.

References: [1] Y. Yamamoto, N. Asao, Chem. Rev. (Washington, DC, U. S.) 1993, 93, 2207-2293. [2] O. T. Summerscales, X. Wang, P. P. Power, Angew. Chem., Int. Ed. 2010, 49, 4788-4790. [3] B. E. Eichler, L. Pu, M. Stender, P. P. Power, Polyhedron 2001, 20, 551-556. [4] K. M. Krebs, J. Wiederkehr, J. Schneider, H. Schubert, K. Eichele, L. Wesemann, Angew. Chem., Int. Ed. 2015, early view.

Poster presentation - P064

Reversibility in reactions of cyclic distannenes with terminal alkynes under ambient conditions Julia Schneider, Jens Henning and Lars Wesemann* [email protected] Institut für Anorganische Chemie, Universität Tübingen Auf der Morgenstelle 18, 72076 Tübingen, Germany Cycloaddition reactions of unsaturated molecules represent an important reaction class in organic chemistry. While thermal [2+2] cycloadditions are mostly symmetry forbidden for classic organic compounds according to the Woodward-Hoffmann rules, the heavier group 14 alkene homologues show examples of reactions with alkynes under ambient conditions.[1] Moreover, the reaction of the stannylene Sn[CH(SiMe3)]2 with a strained alkyne[2] and the reactions of Power’s distannynes with ethylene[3] show reversibility. Here we present the reactivity of distannenes 1 and 2 towards terminal alkynes, leading to the formal [2+2] cycloaddition products 3-5. Interestingly, distannene 1 reacts reversibly at ambient temperature with trimethylsilylacetylene and phenylacetylene in aromatic solvents, while distannene 2 shows an irreversible reaction with phenylacetylene under the same reaction conditions (Figure 1). Experimental and computational studies to further investigate the observed behavior are presented and discussed.

Figure 1. Reaction of distannene 1 and 2 with terminal alkynes (Mes = 2,4,6trimethylphenyl).

References: [1] a) A. Krebs, A. Jacobsen-Bauer, E. Haupt, M. Veith, V. Huch, Angew. Chem. 1989, 101, 640–642. b) Weidenbruch, A. Schäfer, H. Kilian, S. Pohl, W. Saak, H. Marsmann, Chem. Ber. 1992, 125, 563– 566. c) V. Y. Lee, T. Fukawa, M. Nakamoto, A. Sekiguchi, B. L. Tumanskii, M. Karni, Y. Apeloig, J. Am. Chem. Soc. 2006, 128, 11643–11651. [2] L. R. Sita, R. D. Bickerstaff, J. Am. Chem. Soc. 1988, 110, 5208–5209. [3] Y. Peng, B. D. Ellis, X. Wang, J. C. Fettinger, P. P. Power, Science 2009, 325, 1668–1670.

Poster presentation - P065

C,N-Chelated Organotin(IV) Azides as Precursors for Substituted Tetrazoles Petr Švec,

arel Bartoš, Zdeňka Růžičková, Aleš Růžička [email protected]

Department of General and Inorganic Chemistry, University of Pardubice Studentská 573, CZ-53210, Pardubice, Czech Republic Last year we described the preparation and structural characterization of two mixed organotin(IV) amido-azides bearing either C,N-chelating and/or bulky amido ligands.[1] These species were prepared by the reaction of starting stannylene with trimethylsilyl azide via the oxidative addition. Meanwhile we have also synthesized and structurally characterized some other C,N-chelated organotin(IV) azides using the substitution protocol (i.e. reaction of an organotin(IV) chloride with excess NaN3). These species may be employed within the click chemistry.[2] Corresponding tetrazoles are thus formed when mentioned C,N-chelated organotin(IV) azides react towards various substituted acetonitriles (see Figure). The presentation will discuss both synthetic details and structural characterization (NMR spectroscopy, XRD analysis) of prepared tetrazoles bearing triorganotin(IV) moieties.

Figure 1. Reactivity of C,N-chelated organotin(IV) azides towards acetonitrile (R = n-Bu, Ph).

Acknowledgements: The authors would like to thank the Czech Science Foundation (project P207/12/0223) for the financial support of this work. References: [1] P. Švec, Z. Padělková, M. Alonso, F. De Proft, A. Růžička, Can. J. Chem., 2014, 92, 434. [2] H. C. Kolb, M. G. Finn, K. B. Sharpless, Angew. Chem. Int. Ed., 2001, 40, 2004.

Poster presentation - P066

Preparation and Reactivity of Cationic Germanium(II) and Tin(II) Donor-Acceptor Complexes Paul A. Gray*, Brian O. Patrick, and Neil Burford [email protected] Department of Chemistry, University of Victoria P.O. Box 3065, Stn. CSC Victoria, BC V8W3V6 Canada Phosphines and amines represent archetypal ligands in transition metal chemistry, and their complexes are typically depicted involving a Lewis acid-base interaction. Like transition metals, many cationic p-block centres, some of which bear lone pairs, can also act as acceptors to Lewis bases and we have previously shown this to be especially true for cationic group 15 complexes.1 However, the analogous lone-pair bearing cations of the group 14 elements have not been comprehensively studied. Neutral group 14 compounds featuring lone pairs have been shown to react with a variety of small molecules,2 and the reactivity of the corresponding cations represents an attractive extension of this chemistry. We now present the results of our investigation into the synthesis, structure, and characterization of a series of Ge(II) and Sn(II) cations featuring donor-acceptor interactions with amines and phosphines. The structural parameters of neutral, mono-, and dicationic complexes, will be presented, and will be rationalized using computational results. These complexes will also be compared to other cationic, lone pair-bearing p-block complexes, showing clear trends across the main group. Additionally, further reactivity of these cations, including examining their coordination chemistry and reactions with small molecules will be presented.

References: (1) A. P. M. Robertson, P. A. Gray, N. Burford, Angew. Chem. Int. Ed., 2014, 53, 6050 (2) J. D. Erickson, J. C. Fettinger, P. P. Power, Inorg. Chem. 2015, 54, 1940.

Poster presentation - P067

Versatile precursors: Organotin(IV) hydrides as building blocks for low-valent tin chemistry Christian P. Sindlinger, Lars Wesemann* [email protected] Institut für Anorganische Chemie, Eberhard Karls Universität Auf der Morgenstelle 18, GER-72076, Tübingen Compared to organotin monohydrides the chemistry of organotin di- and trihydrides has been scarcely investigated. The release of dihydrogen or a synthetic equivalent from Sn(IV) hydrides offers a clean route toward the generation of the highly reactive organic tin(II) compounds.[1a,b] We investigated selective dehydrogenations of bulky substituted organotin di- and trihydrides applying a catalytic (A, Scheme 1) and a stoichiometric (B) approach to form stannylenes and organotin(II) hydrides.[1c,d] Depending on the conditions clean access to tin-tin coupling products or a variety of low-oxidation state tin compounds or their monomeric base-adducts is realized. First results for the applicability of the concept as well as recent attempts to understand the dehydrogenation process will be presented. Furthermore, the adducts of Nheterocyclic carbenes to stannylenes and organotin(II) hydrides obtained from approach B reveal intriguing properties and have been tested on their applicability as ligands in zero-valent platinum group coordination chemistry. A transfer of the carbene onto the metal is observed, providing the stannylene in the metal coordination sphere.[2] Examples for complexes featuring cyclic structural motifs of novel Sn(II)-M interactions are described.

Figure 1. Catalytic (A) and stoichiometric (B) dehydrogenation approaches on organotin(IV) hydrides and examples for the reactivity of their deriatives.

Acknowledgements: The Fonds der chemischen Industrie and the Studienstiftung d. dt. Volkes are gratefully acknowledged References: [1] (a) X. Fu, W.P. Neumann, J. Organomet. Chem. 1984, C4. (b) C. P. Sindlinger, L. Wesemann, Chem.Sci, 2014, 5, 2739; (c) B. E: Eichler, P. P. Power, J. Am. Chem. Soc, 2000, 122, 8785; (d) E. Rivard et al, J. Am. Chem. Soc, 2007, 129, 16197. [2] C. P. Sindlinger et al., Angew. Chem. In. Ed., 2015, 54, 4087.

Poster presentation - P068

Carbene-Stabilized P(I) Cations Justin F. Binder, Ala’aeddeen Swidan, Martin Tang, Jennifer H. Nguyen, Charles L.B. Macdonald* [email protected] Department of Chemistry and Biochemistry, University of Windsor 401 Sunset Ave., N9B 3P4, Windsor, ON, Canada The discovery of phosphamethine cyanine dyes was a landmark for main group and phosphorus chemistry in that they were among the first cases of molecules containing dicoordinate phosphorus centers and they were the first salts in which P-C π bonding had been observed at ambient temperature.[1] Our group has developed a reliable and high-yield new route to this important class of compounds through a more convenient synthetic pathway: the reaction of carbenes with readily prepared triphosphenium precursors.[2] This reaction template has already shown success for a variety of relatively stable carbene types (Figure 1) and the result is a growing library of new compounds which show promise as functional dyes and as ligands for organometallic chemistry.[3] Experimental and theoretical approaches to assessing the properties and reactivities of these electron-rich phosphorus compounds are presented.

Figure 1: Synthesis of carbene-stabilized P(I) salts.

References: [1] P. Jutzi, Angew. Chem. Int. Ed. Eng., 1975, 14, 232. [2] B.D. Ellis, C.A. Dyker, A. Decken, C.L.B Macdonald, Chem. Commun., 2005, 1965. [3] J.F. Binder, A. Swidan, M. Tang, J.H. Nguyen, C.L.B. Macdonald, Chem. Commun., 2015, DOI: 10.1039/C5CC00331H

Poster presentation - P069

The Reactivity of Heavy Group 15 Allyl Analogs Alexander Hinz, Axel Schulz,* Alexander Villinger [email protected] Department of Chemistry, University of Rostock Albert-Einstein-Straße 3a, GER-18059, Rostock Group 15 analogs of allyl anions, [R–E1E2E3–R]–, are of immanent interest to current research due to the variability of the bulkiness of both organic substituents and potential redox activity. Only recently, hetero-dipnicta-diazanes, e.g. cyclic [ClP(µNTer)2AsCl] and [ClSb(µ-NTer)2BiCl] or open-chain [Ter–N(SbCl2)PN–Ter] and [Ter–NP(Cl)2NN–Ter] were obtained utilizing metathesis reactions of the allylanalogs [Ter–NNN–Ter]–, [Ter–NPN–Ter]–, and [Ter–NSbN–Ter]– (Ter = 2,6dimesitylphenyl) with pnictogen chlorides.[1] The more sophisticated allyl analogs [R– NPP–R]Li and [R–PAsP–R]Li (Mes* = 2,4,6-tri-tertbutyl-phenyl) are known to be highly sensitive compounds, their reactivity is only scarcely investigated.[2] To explore the limits of the salt metathesis route we envisaged the synthesis of a cyclobutane derivative incorporating four different pnictogens via the [R−NAsP−R] − anion. This allyl-analog was not accessible with Ter substituents, hence Mes* was utilized. Computations predicted the biradicaloid long-bond NAsPSb heterocyclus as more stable compared to the [1.1.0]bicyclic short-bond isomer.

Figure 1. Synthetic approach towards the NPAsSb heterocyclus.

Acknowledgements: Financial support by DFG (SCHU 1170/ 11-1) is gratefully acknowledged. References: [1] (a) A. Hinz, A. Schulz, A. Villinger, Angew. Chem. Int. Ed. 2014, 54, 668; (b) A. Hinz, A. Schulz, A. Villinger, J.-M. Wolter, J. Am. Chem. Soc. 2015, DOI 10.1021/jacs.5b00959. [2] (a) E. Niecke, B. Kramer, M. Nieger, Organometallics 1991, 10, 10; (b) L. S. H. Dixon, L. K. Allen, R. J. Less, D. S. Wright, Chem. Commun. 2014, 50, 3007.

Poster presentation - P070

PCO− as a Precursor to Novel P-Containing Heterocycles Thomas P. Robinson, Jose M. Goicoechea* [email protected] University of Oxford, Oxford 12 Mansfield Rd, Oxford, OX1 3TA, UK The phosphaethynolate (PCO-) has been shown to react with electronically unsaturated small organic molecules to yield a variety of P-containing heterocycles.[12] We now show that the reaction between PCO- and a cyclotrisilene (cSi3(Tip)4) yields a fully inorganic propellane heterocycle following complete cleavage of the P≡C bond (Figure 1). This species can be decarbonylated through UV-irradiation to yield a novel [PSi3(Tip)4]- ring.[3] Other P-containing heterocycles are accessible through the deprotonation of alkynesubstituted phosphinecarboxamides, which are derived from the reaction between PCO- and propargylamines. These intramolecular cyclisations yield either 5- or 6-membered ring systems, which can be selectively targeted by introducing different substituents onto the propargylphosphinecarboxamide precursor.[4]

Figure 1. Reactivity between PCO− and a cyclotrisilene (Tip = 2, , -triisopropylphenyl).

Acknowledgements: The EPSRC and the University of Oxford for financial support. References: [1] A. R. Jupp, J. M. Goicoechea, Angew. Chem. Int. Ed. 2013, 52, 10064 [2] X. Chen, S. Alidori, F. F. Pushmann, G. Samtiso-Quinones, Z. Benkő, Z. i, G. Becker, H.–F. Grützmacher, H. Grützmacher, Angew. Chem. Int. Ed. 2014, 53, 1641 [3] T. P. Robinson, M. J. Cowley, D. Scheschkewitz, J. M. Goicoechea, Angew. Chem. Int. Ed. 2015, 54, 683 [4] T. P. Robinson, J. M. Goicoechea, Chem. Eur. J. 2015, 21, 5727

Poster presentation - P071

Synthesis and chemical studies of Diaza-phospha-ferrocenophanes Stefan Weller, Rudolf Pietschnig, László Nyulászi, Dietrich Gudat* [email protected] Institute of Inorganic Chemistry, University of Stuttgart Pfaffenwaldring 55, GER-70569, Stuttgart Little is known about the synthesis and chemical properties of diaza-phosphaferrocenophanes[1]. In connection with our studies[2] on electron rich tetraaminodiphosphines[3] we were also interested to see if diaza-phosphaferrocenophanes can be used as building blocks in the synthesis of diphosphines which can be considered to have some potential for the generation of radicals and the study of intramolecular electron transfer processes. Here, we present our newest results. The reaction of substituted diamino-ferrocenes 1 with di- or trihalogenophosphines give either diazaphospha-[3]ferrocenophanes 2 or diaminoferrocenyliden-bis-phosphanes 3. Subsequent reductive coupling of such products allowed us to synthesize aminoferrocenyl-substituted diphosphines 4 or tetraphosphetanes 5, respectively. The reasons which control the different course of the reactions, the structures, and some selected reactions of these products, will be discussed.

Figure 1. Reaction scheme of 1,1'-diaminoferrocene.

References: [1] B. Wrackmeyer, E. V. Klimkina, W. Milius, Z. Naturforsch., 2009, 64b, 1401; (b) B. Wrackmeyer, E. V. Klimkina, W. Milius, Z. Anorg. Allg. Chem., 2010, 784. [2] D. Förster, I. Hartenbach, M. Nieger, D. Gudat, Z. Naturforsch., 2012, 67b, 765; (b) O. Puntigam, D. Förster, N. A. Giffin, S. Burck, J. Bender, F. Ehret, A. D. Hendsbee, M. Nieger, J. D. Masuda, D. Gudat, Eur. J. Inorg. Chem., 2013, 2041. [3] J.-P- Bezombes, P. B. Hitchcock, M. F. Lappert, J. E. Nycz, Dalton Trans, 2004, 499; (b) L. McInnes, K. Müther, V. Naseri, J. M. Rawson, D. S. Wright, Chem. Commun., 2009, 1691

Poster presentation - P072

Ferrocenylene bridged Oligophosphanes Stefan Borucki, Rudolf Pietschnig* [email protected] Institute of Chemistry, University of Kassel, Germany Heinrich-Plett-Str. 40, GER-34132, Kassel In pioneering work molecular oligo- and polyphosphanes were intensively studied by Baudler et al.[1] Electrochemical measurements revealed low oxidation potentials of these kind of compounds to radical cation species. Especially amino substituted diphosphanes facilitate the fragmentation reaction.[2] The combination of oligophosphanes with ferrocene as electron reservoir and redox active backbone, such as II, should support the cleavage of the electron rich P-P bond and generate potentially stable and persistent radicals. Down to the present day only a single triphospha-[3]ferrocenophane[3] is known in literature and their chemistry therefore remains virtually unexplored. We succeeded in synthesizing precursor I starting from the readily available Fc’(PHtBu)2. Owing to the presence of several stereo centers in these molecules, a large number of diastereomers can be expected. Interestingly, the formation of stereoisomers can be controlled in a certain degree by a combination of ring and steric constraints.[4] Furthermore, this concept has been extended to other phosphorus containing [3]ferrocenophanes involving other heteroatoms.

Figure 1. Precursor I und dimer II, which can possibly be oxidized to radical cation species.

Acknowledgements: Financial support by the Deutsche Forschungsgemeinschaft and ERA Chemistry is gratefully acknowledged (PI 353/8-1). References: [1] Selected reviews: (a) M. Baudler, K. Glinka, Chem. Rev., 1993, 93, 1623; (b) Chem. Rev., 1994, 94, 1273. [2] (a) Review: P.P. Power, Chem. Rev., 2003, 103, 789; (b) M.F. Lappert, J.E. Nycz, Dalton Trans., 2004, 499. [3] A.G. Osborne, H.M. Pain, M.B. Hursthouse, M.A. Mazid, J. Organomet. Chem., 1993, 453, 117. [4] C. Moser, F. Belaj, R. Pietschnig, Chem. Eur. J., 2009, 15, 12589.

Poster presentation - P073

N-Heterocyclic Carbene Phosphinidene and Phosphinidyne Metal Complexes and their Applications Adinarayana Doddi, Dirk Bockfeld and Matthias Tamm* [email protected] Institute of Inorganic and Analytical Chemistry, Technical University Braunschweig Hagenring 30, 38106 Braunschweig, Germany Phosphinidenes (R‒P, analogs of carbenes and nitrenes) are a fascinating class of highly reactive low-valent main-group compounds. They possess unique bonding, reactivity and structural diversity.[1] Therefore, the electronic tuning of such phosphorus reagents using different ancillary ligands is an intriguing and challenging not only from synthetic point of view but also understanding of their chemical properties. Transition (and also main-group metal) complexes of such novel ligands could display applications in the small molecule activation as well as in homogeneous catalysis. Recently, our group has developed a novel method for isolation of an Nheterocyclic carbene supported novel phosphinidene (IPr=P‒SiMe3) (Figure 1) and it was introduced as a synthon for the preparation of terminal carbene–phosphinidyne transition metal complexes of the type [(IPr=P)ML n ] (ML n =(η6-p-cymene)RuCl and (η5-C5Me5)RhCl) (i.e, Figure 1). Their spectroscopic and structural characteristics show their similarity with arylphosphinidene complexes.[2] The formally mono negative “IPr=P” ligand is also capable of bridging two or three metal atoms as demonstrated by the preparation of bi- and trimetallic RuAu, RhAu, Rh2, and Rh2Au complexes.[3a] Furthermore, several homo and bi metallic coinage metal complexes of carbene-phosphinidene adduct were isolated.[3b] The newly synthesized cationic dual gold complexes were found highly active homogeneous catalysts and highlights the use of carbene-phosphinidenes as supporting ligands. In this presentation, syntheses, bonding and applications of this new class of formally phosphorus (I) reagents will be discussed.

Figure 1. Synthesis of a carbene-phosphinidyne transition metal complex.[3a]

References: [1] (a) O. Back, M. H. Ellinger, C. D. Martin, D. Martin, G. Bertrand, Angew. Chem. Int. Ed. 2013, 52, 2939–2943. (b) G. Frison, A. Sevin, J. Organomet. Chem, 2002, 643–644, 105-111. [2] H. Aktaş, J. C. Slootweg, . ammertsma, Angew. Chem. Int. Ed. 2010, 49, 2102-2113. [3] (a) A. Doddi, D. Bockfeld, T. Bannenberg, P. G. Jones, M. Tamm, Angew. Chem. Int. Ed. 2014, 53, 13568 –13572. (b) A. Doddi, D. Bockfeld, A. Nasr and M. Tamm, manuscript in preparation.

Poster presentation - P074

NEW SYNTHETIC APPROACH TO THE SYNTHESIS OF NHCPHOSPHINIDENE COMPOUNDS Otfried Lemp, Carsten von Hänisch [email protected] Department of Chemistry, Philipps-Universität Marburg Hans-Meerwein-Straße 4 35032 Marburg Recently, the N-heterocyclic-carbene stabilized parent phosphinidene (PH) was isolated and fully characterized.[1] We present a new synthetic approach to generating such compounds via oxidation of LiPH2with NHC transition metal halides and further reactions of these species, specially with [W(CO)5(thf)]

Figure 1. Crystal Structure of IMes:PHW(CO)5

References: [1] (a) Hansen K..; Szilvási T.; Blom B.; Irran E.; Driess M. Chemistry Eur. J., 2014, 20, 1947. (b) Doddi A.; Bockfeld D.; Bannenberg T.; Jones P. G.; Tamm M. Angew. Chem ,2014, 126, 13789. (c) Tondreau A. M.; Benko Z.; Harmer J. R.; Grützmacher H. Chem. Sci., 2014, 5, 1545.

Poster presentation - P075

Zwitterionic Triphospheniums as Multidentate Donors Stephanie C. Kosnik, G. J. Farrar, C.L.B. Macdonald* [email protected] Department of Chemistry and Biochemistry University of Windsor, 401 Sunset Ave, Windsor, On Canada Triphosphenium cations have a diverse and fruitful history originating from the seminal work of Schmidpeter in the 1980’s.[1] Despite their stability, there are few reports of coordination chemistry involving these compounds, which is most likely a consequence of the presence of reactive anions and perhaps the positive charge on the potential donor.[2] In order to circumvent these issues, we have been interested in the generation of neutral triphosphenium species[3], as it has recently been shown that such neutral species do in fact increase the donating ability of the P1 center.[4,5] Furthermore, the use of an anionic backbone could serve as an alternative donor site, thus increasing the potential utility of these molecules as multidentate donors. The investigations presented herein include: the characterization of complexes with various transition metals and structural assessment of many of these molecules via Xray crystallography.

References: [1] A. Schmidpeter, S. Lochschmidt, W. S. Sheldrick, Angew. Chem. Int. Ed. Engl. 1982, 21, 63–64. [2] B. D. Ellis, C. L. B. Macdonald, Coord. Chem. Rev. 2007, 251, 936–973. [3] S. C. Kosnik, G. J. Farrar, E. L. Norton, B. F. T. Cooper, B. D. Ellis, C. L. B. Macdonald, Inorg. Chem. 2014, 11, 13061–13069. [4] J. W. Dube, C. L. B. Macdonald, P. J. Ragogna, Angew. Chem. Int. Ed. Engl. 2012, 51, 13026–30. [5] J. W. Dube, C. L. B. Macdonald, B. D. Ellis, P. J. Ragogna, Inorg. Chem. 2013, 52, 11438–49.

Poster presentation - P076

Synthesis and Photophysical Properties of Novel PhosphorusContaining Conjugated Systems Alicia López-Andarias, Philip Hindenberg, Carlos Romero-Nieto* [email protected] Organisch-Chemisches Institut, University of Heidelberg Im Neuenheimer Feld 270, Room 270, GER-69120, Heidelberg In the last decades, the design and development of novel multifunctional materials based on heterocyclic compounds has become an important research topic. The introduction of heteroatoms into π-conjugated molecules enables modulating the HOMO and LUMO energy levels and thus tailoring the optoelectronic properties. In this context, phosphorus heterocycles offer unique means to keep control over the photophysics of π-conjugated materials. As a matter of fact, orbital interactions between the phosphorus centers and the π-system give rise to a low-lying LUMO and, therefore, to an acceptor character.[1] Moreover, phosphorus atoms provide selective centers for reversible post-functionalization reactions with transition metals, Lewis acids, oxidizing and alkylating agents.[2] Recently, phosphorus-based systems have emerged as promising luminescent materials with outstanding properties.[1] This chemistry is, however, at its early stage; exploring the full potential of phosphorus heterocycles requires certainly the development of new architectures. In this communication, we will present the synthesis and properties of novel, fused phosphorus-containing systems. We will report a detailed study on the photoelectrochemical features of our new phosphorus-based heterocycles. Moreover, we will discuss the impact of extending the π-conjugation through different heteroaromatics into the optoelectronic properties.

Acknowledgements: Financial support by the Fonds der Chemischen Industrie, Germany, is gratefully acknowledged. We also thank the Organisch-Chemisches Institut, Universität Heidelberg, Germany, for its support. References: [1] T. Baumgartner, Acc. Chem. Res., 2014, 47, 1613-1622. [2] Y. Matano, A. Saito, T. Fukushima, Y. Tokudome, F. Suzuki, D. Sakamaki, H. Ito, K. Tanaka, H. Imahori, Angew. Chem. Int. Ed., 2011, 50, 8016-8020.

Poster presentation - P077

Cycloaddition of P–C Single Bonds? The Case of Oxaphosphirane Complexes and ortho-Benzochinones Payal Malik,(a) Arturo Espinosa,* (b) Gregor Schnakenburg, (a) and Rainer Streubel*(a) [email protected] (a) Institut für Anorganische Chemie der Rheinischen Friedrich-WilhelmsUniversität Bonn, Gerhardt-Domagk-Strasse 1, 53121 Bonn (Germany) (b) epartamento de u mica rgánica, acultad de u mica, Universidad de Murcia, Campus de Espinardo, 30100, Spain Due to their P=C double bond, phosphaalkenes have been used as versatile building blocks in organic synthesis,[1] catalysis[2] and polymer[3] chemistry; one example is their [4+2] cycloaddition with ortho-benzochinones. The latter are also known to react with tertiary phosphanes in [4+1] cycloaddition reactions due to the P-lone pair.[4] In contrast, P–C single bonds are known to be inert towards cycloaddition reactions. To address the quest of P–C single bond reactivity towards cycloaddition reactions, investigations were launched, recently, focusing on endocyclic P–C bonds of heterocyclic ligands. Herein, reactions of oxaphosphirane complexes with tetrachloro ortho-benzochi-none are reported together with DFT calculations of reaction pathway dependencies on redox potentials. The obtained 1,3,6,2-trioxaphospha-heptane complexes 1–3 were fully characterized by IR, 1H, 13C, 31P NMR and single crystal X-ray diffraction techniques.[5]

Scheme 1. Reactions of oxaphosphirane complexes with tetrachloro ortho-benzochinone.

Acknowledgements: This work was financially supported by the Deutsche Forschungsgemeinschaft (SFB 13 “Chemistry at Spin Centers”). References: [1] (a) F. Mathey, Chem. Rev.,1990, 90, 997–1025; (b) M. Regitz, Chem. Rev., 1990, 90, 191–213. [2] P. L. Floch, Coord. Chem. Rev.,2006, 250, 627–681. [3] J. I. Bates, J. Dugal-Tessier, D. P. Gates, Dalton Trans., 2010, 39, 3151–3159. [4] (a) T. Gust, W.-W. du Mont, R. Schmutzler, C. G. Hrib, C. Wismach, P. G. Jones, Phoshorus, Sulfur. Silicon Relat. Elem., 2009, 184, 1599–1611; (b) L. Weber, Eur. J. Inorg. Chem., 2000, 2425– 2441. [5] P. Malik, G. Schnakenburg, A. Espinosa, R. Streubel, submitted.

Poster presentation - P078

Reactions of the Pentelidene Complexes [Cp*E{W(CO)5}2] (E = P, As) with Heterocumulenes Michael Seidl, Manfred Scheer* [email protected] Institute of Inorganic Chemistry, University of Regensburg Universitätsstraße 31, GER-93053, Regensburg Phosphinidenes (R–P) are low-valent organophosphorus compounds containing 6 valence electrons which are unstable as ‘free’ molecules. They can be stabilized on transition-metal fragments by various ways. Our research interest is dedicated to bridging pentelidene complexes of the type [Cp*E{W(CO)5}2] (E = P, As; Cp* = C5Me5) due to their high diversity in reactivity. These complexes show interesting reaction behavior under thermolytic[1] and photolytic[2] conditions. They also reveal high reactivity towards nucleophiles like isonitriles.[3] The reactivity of the pentelidene complexes towards heterocumulenes, like cabodiimides, alkylazides and carboimidophosphenes will be presented. The carbodiimides and the alkylazides react with the pentelidene complexes by a 1,3-cycloaddition to form novel four membered heterocycles like the triazaphosphete complexes.[4] The reaction with the carboimidophosphene leads not to such heterocycles, however the first example of a 1,3-butadiene analog is obtained consisting only of mixed heavier Group 15 elements.

Figure 1. Reactions of the pentelidene complexes with heterocumulenes. Acknowledgements: Deutsche Forschungsgemeinschaft (DFG). References: [1] M. Scheer, E. Leiner, P. Kramkowski, M. Schiffer, G. Baum, Chem. Eur. J. 1998, 4, 1917-1923. [2] M. Scheer, C. Kuntz, M. Stubenhofer, et al, Angew. Chem. Int. Ed. 2009, 48, 2600-2604. [3] M. Seidl, M. Schiffer, M. Bodensteiner, A. Y. Timoshkin, M. Scheer, Chem. Eur. J. 2013, 19, 13783-13791. [4] M. Seidl, C. Kuntz, M. Bodensteiner, A. Y. Timoshkin, M. Scheer, Angew. Chem. Int. Ed. 2015, 54, 2771-2775.

Poster presentation - P079

1,3,2-Dioxaphosphol-4-enes: synthesis of a novel inorganic ring system Philip Junker, Vitaly Nesterov, Rainer Streubel [email protected] Institut für Anorganische Chemie der Rheinischen Friedrich-Wilhelms-Universität Bonn Gerhard-Domagk-Str. 1, GER-53121 Bonn The first synthesis of a σ4λ5-oxaphosphirane was described by Röschenthaler in 1978,[1] whereas σ3λ3-oxaphosphiranes still remain unknown. In contrast, their transition metal(0) complexes, first reported by Mathey in 1990, have been synthesized via epoxidation of phosphaalkene complexes,[2] or via phosphinidene complex transfer reaction onto aldehydes as described by Streubel et al.[3] But a broader investigation was hampered until the advent of new protocol: the reaction of Li/Cl phosphinidenoid complexes 2 and carbonyls at low temperature, which was reported in 2007 by Streubel et al.[4] Since then a wealth of new structures were established departing from oxaphosphirane complexes, including the first C-acyloxaphosphirane complex 3[5] obtained via reaction of 2 with a α,β-diketone (Scheme). While a derivative of 3 was obtained in good yields, complex 4 having a novel 1,3,2dioxaphosphol-4-ene ligand was obtained as by-product, only, and the pathway could not be clarified. Herein, detailed investigation on syntheses of novel C-acylsubstituted oxaphosphirane and 1,3,2-dioxaphospholene complexes 3,4 will be presented, including a facile protocol for 4.

Acknowledgements: This work was financially supported by the DFG (STR 411/26-3 and 411/29-1), and it is dedicated to Prof. F. Mathey References: [1] G. V. Röschenthaler, K. Sauerbrey, R. Schmutzler Chem. Ber. 1978, 111, 3105. [2] S. Bauer, A. Marinetti, L. Ricard, F. Mathey, Angew. Chem. Int. Ed. Engl. 1990, 29, 1166. [3] R. Streubel, A. Kusenberg, J. Jeske, P. G. Jones, Angew. Chem. Int. Ed. Engl. 1994, 33, 2427. [4] a) A. Özbolat, G. von Frantzius, M. Nieger, R. Streubel, Angew. Chem. Int. Ed. Engl. 2007, 46, 9327; b) R. Streubel, M. Bode, J. M. Pérez, G. Schnakenburg, J. Daniels, M. Nieger, P. G. Jones, Z. Anorg. Allg. Chem. 2009, 635, 1163; c) M. Bode, J. Daniels, R. Streubel, Organometallics 2009, 28, 4636. [5] L. Abdrakhmanova, G. Schnakenburg, A. Espinosa, R. Streubel, Eur. J. Inorg. Chem. 2013,1727. [6] V. Nesterov, P. Junker, G. Schnakenburg, R. Streubel, manuscript in preparation.

Poster presentation - P080

Synthesis of asymmetric phosphorus diiminopydrine complexes Siu Kwan Lo and Jose M Goicoechea* [email protected] Department of Chemistry, Chemistry Research Laboratory, University of Oxford 12 Mansfield Rd, Oxford, OX1 3TA, UK The development of geometry-constrained catalysts using pincer ligand scaffolds has received significant attention in the field of organometallic chemistry. However species in which such ligands are used in the immediate coordination sphere of maingroup elements, such as phosphorus, are much rarer. Three-coordinate complexes of phosphorus(III) generally exhibit trigonal monopyramidal geometries due to the presence of a stereochemical lone pair (minimizing interelectronic repulsion according to VSEPR theory). Constrains such systems in ‘T-shaped’ geometries by using planar pincer ligands can be used as a strategy to access molecules with two orthogonal orbitals (one filled: lone pair; one empty: typically stabilized via π-interactions) which in principle should allow for the heterolytic cleavage of small molecule substrates.[1] We have recently observed that reaction of PCl3 with an α,α’-diiminopyridine ligand (L) in dichloromethane results in clean formation of the phosphorus-centered complex [1][Cl] (see Scheme 1). This observation is in contrast with previously reported observations on the reactivity of other phosphorus(III) halides with L.[2] Activation of one of the C–H bonds of an imino methyl group and subsequent reduction of the other imine group in the α,α’diiminopyridine has been observed. 1 has been studied extensively by X-ray crystallography, 1H and 31P NMR spectroscopy. Reactivity studies on this product, and other related main-group systems, are currently on-going.

Scheme 1

Acknowledgements: We thank the University of Oxford for financial support of this research. References: [1] (a) N. L. Dunn, A. T. Radosevich, J. Am. Chem. Soc. 2012, 134, 11330. (b) S. M. McCarthy, Y.-C Lin, D. Devarajan, J. W. Chang, H. P. Yennaway, R. M. Rioux, D. H. Ess, A. T. Radosevich, J. Am. Chem. Soc. 2014, 136, 4640. [2] C. D. Martin, P. J. Ragogna, Dalton Trans., 2011, 40, 11976.

Poster presentation - P081

Synthesis, thermolysis and photochemistry of oxaphosphirane complexes Melina Klein, Rainer Streubel* [email protected] Institut für Anorganische Chemie, Rheinischen-Friedrich-Wilhelms-Universität Bonn Gerhard-Domagk-Str. 1, GER-53121 Bonn Oxaphosphirane complexes are known since the nineties but a broad development of the chemistry was hampered by low yield methodologies.[1] This changed recently as a new facile protocol was reported,[2] enabling the systematic study of a broad range of oxa-phosphirane complexes, obtained under mild conditions and with high diastereoselectivity. Herein, we describe synthesis of oxaphosphirane complexes bearing donor substituents[3] at the ring carbon atom as well as investigations on their thermolysis and photochemistry. For example, a thermal ring‑expansion of 2 was discovered leading to the new chelate complexes 3 (route A) and irradiation to complexes 4 representing a dimer‑like product (route B).[4] Preliminary investigations on reactions of 1 with NHC 5 (route C) revealed formation of complexes 6, which were used to establish a novel pathway to oxaphosphirane complexes 2.

Acknowledgements: We are grateful to the SFB 13 „Chemistry at Spin Centers“, the DFG (STR 411/29-1) and the DAAD (PPP with Canada/stay of M.K.) for financial support. References: [1] (a) S. Bauer, A. Marinetti, L. Ricard, F. Mathey, Angew. Chem. Int. Ed. Engl. 1990, 29, 1166– 1167; (b) R. Streubel, A. Kusenberg, J. Jeske, P. G. Jones, Angew. Chem. Int. Ed. Engl. 1994, 33, 2427–2428; [2] (a) A. Özbolat, G. von Frantzius, J. M. Pérez, M. Nieger, R. Streubel, Angew. Chem. Int. Ed. Engl. 2007, 46, 9327–9330; (b) M. Bode, J. Daniels, R. Streubel, Organometallics 2009, 28, 4636–4638; (c) R. Streubel, M. Bode, J. Marinas Pérez, G. Schnakenburg, J. Daniels, M. Nieger, P. G. Jones, Z. anorg. allg. Chem. 2009, 635, 1163–1171; (d) C. Albrecht, M. Bode, J. M. Pérez, J. Daniels, G. Schnakenburg, R. Streubel, Dalton Trans. 2011, 40, 2654–2665; [3] (a) R. Streubel, M. Klein, G. Schnakenburg, Organometallics 2012, 31, 4711–4715; (b) M. Klein, C. Albrecht, G. Schnakenburg, R. Streubel, Organometallics 2013, 32, 4938–4943; [4] M. Klein, G. Schnakenburg, R. Streubel, to be published.

Poster presentation - P082

Fluorinated oxaphosphirane complexes: synthesis, redox potentials and novel reactions C. Murcia García, A. Espinosa Ferao, A. Frontera and R. Streubel* [email protected] Inorganic Chemistry, University of Bonn Gerhard-Domagk-Str. 1, GER-53121 Bonn. Facile access to oxaphosphirane complexes was achieved, recently, using the broadly applicable synthetic protocol based on the reaction of Li/Cl phosphinidenoid complexes 1 with carbonyl derivatives.[1,2] The interest of tuning the reactivity of oxaphosphirane complexes prompted us to synthesize new derivatives bearing electronwithdrawing groups at carbon, in combination with a potential leaving group with the required bulkiness at phosphorus, i.e. the triphenylmethyl group.[3] Herein, synthesis of fluorinated derivatives 2a-d [4] their acid induced ring-expansion reaction to give 4 [5,6] as well as an unexpected outcome (3) of the reaction between complex 1 (M = Mo) and benzophenone[7] are presented. Preliminary experiments aiming at transient complexes 5a-d via reductive SET reactions as well as theoretical calculations and results of cyclic voltammetry measurements will be discussed.

Figure 1. Synthesis and reactions of fluorinated oxaphosphirane complexes

References: [1] a) A. Özbolat, G. von Frantzius, J. M. Pérez, M. Nieger, R. Streubel, Angew. Chem. Int. Ed. 2007, 46, 9327-9330; b) R. Streubel, A. Özbolat-Schön, G. v. Frantzius, H. Lee, G. Schnakenburg, D. Gudat, Inorg. Chem. 2013, 52, 3313-3325. [2] V. Nesterov, G. Schnakenburg, A. Espinosa, R. Streubel, Inorg. Chem. 2012, 53, 12343-12349. [3] C. Murcia García, A. Bauzá, G. Schnakenburg, A. Frontera, R. Streubel, Cryst. Eng. Com. 2015, 17, 1769-1772. [4] A. Espinosa, R. Streubel, Chem. Eur. J. 2012, 18, 13405-13411. [5] J. M. Pérez, H. Helten, G. Schnakenburg, R. Streubel, Chem. Asian J. 2011, 6, 1539–1545. [6] C. Murcia García, R. Streubel, manuscript in preparation. [7] C. Murcia García, A. Espinosa Ferao, R. Streubel, manuscript in preparation.

Poster presentation - P083

Bimetallic 1,3 Diphosphacyclobutadiene Sandwich Compounds Christian Rödl and Robert Wolf* [email protected] Institute of Inorganic Chemistry, University of Regensburg Universitätsstraße 31, D-93040, Regensburg Bis(1,3-diphosphacyclobutadiene) sandwich complexes of type [Co(η4-P2C2R2)2]− are readily prepared by reacting phosphaalkynes with the cobalt(-I) complex [Co(anthracene)2]−.[1] Their ability to coordinate further metal atoms through the phosphorus lone pairs potentially gives access to new oligonuclear complexes and supramolecular coordination compounds.[2,3] Recently, we reported the preparation of a series of copper(I), silver(I) and gold(I) complexes of our [Co(η4-P2C2R2)2]− anions. The resulting bimetallic compounds feature distinct structures that range from simple molecular 1:1 complexes to coordination polymers and supramolecular assemblies, e.g. the molecular square [Au{Co(P2C2tBu2)2}]4.[3] Here, we present an extension of these studies to group 9 and 10 metals. The new dinuclear complexes [(η4C4Me4)Co(CO)2{Co(η4-P2C2tBu2)2}] (1) and [CpNi(PPh3){Co(η4-P2C2tBu2)2}] (2) have been synthesized by transmetalation of [Tl(thf)2{Co(P2C2tBu2)2}] with [(C4Me4)Co(CO)2I] and [CpNiBr(PPh3)]. Compounds 1 and 2 have been characterized by single-crystal X-ray diffraction and spectroscopic techniques. The cyclic voltammograms of 1 and 2 feature similar reversible redox waves at E1/2 = −0.1 V for 1 and E1/2 = −0.1 V for 2 (vs. Fc/Fc+ in THF/TBAH). The experimental results are supported by DFT calculations which give additional insight into the electronic structures of the investigated complexes.

Figure 1. Synthesis of the new dinuclear complexes 1 and 2. References: [1] a) R. Wolf, A. W. Ehlers, J. C. Slootweg, M. Lutz, D. Gudat, M. Hunger, A. L. Spek, K. Lammertsma, Angew. Chem. Int. Ed. 2008, 47, 4584–4587; Angew. Chem. Int. Ed. 2009, 48, 3104– 3107; b) R. Wolf, A. W. Ehlers, M. M. Khusniyarov, F. Hartl, B. de Bruin, G. J. Long, F. Grandjean, F. M. Schappacher, R. Pöttgen, J. C. Slootweg, M. Lutz, A. L. Spek, K. Lammertsma, Chem. Eur. J. 2010, 16, 14322–14334. [2] review on diphosphacyclobutadiene complexes: A. Chirila, R. Wolf, J. C. Slootweg, K. Lammertsma, Coord. Chem. Rev. 2014, 270, 57–74. [3] a) J. Malberg, T. Wiegand, H. Eckert, M. Bodensteiner, R. Wolf, Chem. Eur. J. 2013, 19, 2356– 2369; Eur. J. Inorg. Chem. 2014, 1638–1651; c) J. Malberg, M. Bodensteiner, D. Paul, T. Wiegand, H. Eckert, R. Wolf, Angew. Chem. Int. Ed. 2014, 53, 2771–2775.

Poster presentation - P084

Oxidation and Isomerization of 1,3-Diphosphete Complexes Eva-Maria Rummel, Manfred Scheer* [email protected] Institute of Inorganic Chemistry, University of Regensburg Universitätsstraße 31, GER-93040 Regensburg Although 1,3-diphosphacyclobutadiene (1,3-diphosphete) complexes have first been isolated as early as 1986 by the Nixon and Regitz groups simultaneously,[1] these kind of complexes are still of interest regarding their coordination behaviour, as current literature shows.[2] However, as calculations show, the 1,2-diphosphete isomer should always be the thermodynamically and kinetically favourable isomer.[3] This work shows the 1,3-diphosphete complexes [(CpꞌꞌꞌCo)n(η4-C2P2R2)] (n = 1: R = tBu (1), iPr (2); n = 2: R= Me (3)) being reacted with Ag[Al{OC(CF3)}4] (= Ag(pftb)) to form either oxidized species [(CpꞌꞌꞌCo)2(η4-C2P2Me2)]+[pftb]- (4) or isomerize to form novel 1,2-diphosphete coordination complexes of silver(I): ([{(CpꞌꞌꞌCo)(η4C2P2R2)}nAg2]2+·2[pftb]- (n = 4, R = tBu (5), n = 2, R = iPr (6)).

Figure 1. Isomerization of 1 in the presence of Ag+ to form the 1,2-diphosphete coordination complex 5.

References: [1] a) P. Binger, R. Milczarek, R. Mynott, M. Regitz, W. Rösch, Angew. Chem. Int. Ed., 1986, 25, 644; Angew. Chem., 1986, 98, 645, b) P. B. Hitchcock, M. J. Maah, J. F. Nixon, Chem. Commun., 1986, 737. [2] a) E.-M. Rummel, M. Eckhardt, M. Bodensteiner, E. V. Peresypkina, W. Kremer, C. Gröger, M. Scheer, Eur. J. Inorg. Chem., 2014, 1625. b) J. Malberg, T. Wiegand, H. Eckert, M. Bodensteiner, R. Wolf, Eur. J. Inorg. Chem., 2014, 1638. [3] S. Creve, M. T. Nguyen and L. G. Vanquickenborne, Eur. J. Inorg. Chem., 1999, 1281.

Poster presentation - P085

Structural Properties of Paraben Substituted Fluorenylidene-Double Bridged Cyclophosphazenes Elif Şenkuytu and Gönül enilmez Çiftçi [email protected] Department of Chemistry, Gebze Technical University Gebze 41400, Kocaeli, Turkey Phosphazenes are important family of inorganic systems consist of the repeating units – [N=PR2] – with trivalent nitrogen and pentavalent phosphorus atoms. When the side group “R” is a halogen, it can be replaced with different groups via nucleophilic substitution reactions thus forming phosphazene compounds bearing different properties.[1] Cyclotriphosphazenes could form a core to synthesize a variety of compounds that can be utilized used as biomedical materials, anticancer and antimicrobial agents, liquid crystals and organic light emitting diodes.[2] In the current study, novel cyclotriphosphazene compounds were synthesized and fully characterized by mass spectrometry, 1H and 31P NMR spectroscopies and elemental analysis.

Figure 1. Paraben substituted fluorenylidene-double bridged cyclophosphazenes

Acknowledgements: The authors thank to the Scientific and Technical Research Council of Turkey (TÜBİTA ) for financial support (Project No: 11 Z 1). References: [1] (a) V. Chandrasekhar, M. D. Pandey, B. Das, B. Mahanti, K. Gopal, R. Azhakar, Tetrahedron, 2011, 67, 913 (b) G. enilmez Çiftçi, E. Şenkuytu, E. Tanr verdi Eçik, A. l ç, F. uksel, Polyhedron, 2011, 30, 2227. [2] (a) T. ld r m, . Bilgin, G. enilmez Çiftçi, E. Tanr verdi Eçik, E. Şenkuytu, . Uludağ, . Tomak, A. l ç, Eur. J. Med. Chem, 2012, 52, 213. (b) enilmez Çiftçi, E. Şenkuytu, M. Durmus, F. uksel, A. l c, Dalton Trans, 2013, 42, 14916.

Poster presentation - P086

The synthesis and characterization of spiro bridged cyclophosphazene compounds containing two chiral centers Serap Beşli(a) , Ceylan Mutlu,(a) Fatma Yuksel,(a) Christopher W. Allen(b) [email protected] (a) Department of Chemistry, Gebze Technical University, Gebze-Kocaeli, TURKEY (b) Department of Chemistry, University of Vermont, Vermont 05405-0125, USA N,N-spiro bridged octachlorobiscyclotriphosphazene (1) is a new precursor for the preparation of novel phosphazene derivatives. It is a rigid and stable compound with four PCl2 groups at the corners of two fused cyclophosphazene rings [1,2]. In this study, 1 was reacted with the di-functional reagent, 3-amino-1-propanol, and the chiral compounds (2a, 2b, 3a, 3b) containing two equivalent chiral centres were obtained (Figure 1). All compounds were characterized by elemental analysis, mass spectrometry, 1H and 31P NMR spectroscopy. The stereogenic properties of compounds were investigated by chiral HPLC and 31P NMR spectroscopy in the presence of a chiral solvating agent (CSA).

Figure 1. The reactions of compound 1 with the 3-amino-1-propanol

Acknowledgements: The authors would like to thank the Scientific and Technical Research Council of Turkey for financial support (Grant 113Z304). References: [1] S. Beşli, S. J. Coles, D. B. Davies, A.O. Erkovan, M. B. Hursthouse, A. l ç, Inorg. Chem., 2008, 47, 5042-5044. [2] S. Beşli, S. J. Coles, D. B. Davies, A. l ç, R. A Shaw, Dalton Trans., 2011, 40, 5307-5315.

Poster presentation - P087

Syntheses, structural characterizations of new phosphazenes bearing vanillinato and pendant monoferrocenyl groups asemin Tümer , Nuran Asmafiliz, Zeynel

lç

[email protected] Department of Chemistry, Karabük University Department of Chemistry, Karabük University 78050 Karabük, Turkey Cyclotriphosphazene (N3P3Cl6) is a versatile starting compound for the syntheses of cyclotriphosphazene derivatives, polyorganophosphazenes and dendrimers. Cyclotriphosphazene derivatives with different side groups such as alcohols and amines are attracting increased interest in various areas of technological and medicinal importance.[1] In this study, the gradual Cl replacement reactions of NN spirocyclic monoferrocenyl cyclotriphosphazenes (1-3) with the potassium salt of 4hydroxy-3-methoxybenzaldehyde (potassium vanillinate) resulted in the mono (1a– 3a), geminal (gem-1b–3b), non-geminal (trans-1b–3b), tri (1c and 3c) and tetra (1d– 3d) vanillinato-substituted phosphazenes (Scheme 1). All the phosphazene derivatives have stereogenic P-center(s), except tetra-substituted ones. The structures of the new phosphazene compounds were determined by FTIR, MS, 1H-, 13C- and 31P-NMR spectral data.[2]

Scheme 1 The phosphazene derivatives obtained from the reactions of tetrachloro monoferrocenylphosphazenes with potassium vanillinate.

Acknowledgements: The authors acknowledge the “Scientific and Technical Research Council of Turkey” Grant No.112T0 3. References: [1] Gleria M, Jaeger De, Applicative Aspect of Cyclophosphazenes. Nova Science Publishers, New York, 2004. [2]. . Tümer, . . oc, N. Asmafiliz, Z. l c, T. Hökelek, H. Soltanzade, . Ac k, M. . ola, A. O. Solak, J Biol Inorg Chem, 2015, 20, 165–178.

Poster presentation - P088

The substitution reactions of a mono ansa fluorodioxycyclotriphosphazene derivative with diols Ceylan Mutlu , Serap Beşli, Fatma uksel [email protected] Department of Chemistry Gebze Technical University, Gebze-Kocaeli, TURKEY Nucleophilic substitution reactions are of central in cyclophosphazene chemistry due to the complexity and variability of the reaction mechanisms and the broad range of regio- and stereo- chemical outcomes of these reactions.[1-3] In this work, the reactions of N3P3Cl4[OCH2(CF2)3CH2O] (1) with the disodium salts of 1,3-propandiol and tetraethyleneglycol were investigated in order to determine the reaction pathways and mechanism of nucleophilic substitution at the PCl2 and PCl(OR) phosphorus atoms. The products were characterized by elemental analysis, mass spectrometry, 1H and 31P NMR spectroscopy and X-ray crystallography. The reactions of compound 1 with disodium salt of each diol occurred at the PCl2 group before the fluorodiol bearing P(OR)Cl moiety so the spiro derivatives (2, 3) formed as the major product in each case (Figure 1).

Figure 1. The reactions of compound 1 with the diols.

Acknowledgements: The authors would like to thank Professor Christopher W. Allen (Department of Chemistry, University of Vermont) for helpful discussions. References: [1] C. W. Allen, Chem. Rev., 1991, 91, 119-135. [2] V. Chandrasekhar, V. Krishnan, Adv. Inorg. Chem., 2002, 53, 159-211. [3] S. Beşli, C. Mutlu, F. uksel and A. l ç, Polyhedron, 2014, 81, 777-787.

Poster presentation - P089

Cis- and trans-Azole Substituted Cyclotriphosphazene Derivatives Elif Özcan, Fatma Yuksel, Aylin Uslu* [email protected] Department of Chemistry Gebze Technical University Gebze, 41400, Kocaeli-Turkey Phosphazenes containing a framework of alternating phosphorus and nitrogen atoms are the important class of inorganic compounds. Azole substituted phosphazenes are attractive molecules, because of their tendency to give complexes with various metals[1]. Most phosphazene derivatives can be synthesized via nucleophilic substitution reactions of chlorine atoms on the chlorophosphazene with organic nucleophiles[2]. In this study we have synthesized imidazole and benzimidazole substituted cis- and trans-phenoxy cyclophosphazene derivatives (Figure 1). Compounds (1a,b and 2a,b) have been characterized by mass, 31P, 1H and 13C NMR spectroscopies. Compounds 1a, 2a, 2b have been also determined structurally by Xray crystallography.

Figure 1. Structures of the compounds 1a,b and 2a,b.

References: [1] V. Chandrasekhar, P. Thilagar, B.M. Pandian, Coord. Chem. Rev., 2007, 251, 1045-1074. [2] R. J. Davidson, E. W. Ainscough, A. M. Brodie, G. B. Jameson, M. R. Waterland, H. R. Allcock, M. D. Hindenlang, Polyhedron, 2015, 85, 429-436.

Poster presentation - P090

A new insight into the homolytical bond dissociation of Tetraaminodiphosphines Markus Blum, Johannes Bender, Fabian Ehret, Wolfgang Frey, Sebastian Plebst, Dietrich Gudat* [email protected] Department of inorganic chemistry, University of Stuttgart Pfaffenwaldring 55, GER-70569, Stuttgart Thermally induced, homolytical P-P-bond dissociations are known for Tetraamino-diphosphines with sterically demanding substituents.[1-2] Similar reactivity was found for P,N heterocyclic compounds (Bisdiazaphospholenes).[3] The thermally generated phosphinyl radicals are discussed as intermediates in the reactions of the diphosphines with complexes, white phosphorus, and unsaturated hydrocarbons.[4-5] In this contribution, we describe a study on the thermodynamics of the dissociation of some diphosphines. Dissociation constants (KDiss) were determined from quantitative EPR-Measurements[6] and allowed to calculate dissociation enthalpies (ΔHDiss) and entropies (ΔSDiss). The results highlight importance of steric strain for an easy P-P-bond cleavage.

Figure 1. left: EPR-Signal of (iPr2N)(Me3Si)2NP∙ from 2 0 – 340K, right: Van’t Hoff-plot created from the analysis of the double integrals of the EPR-signals.

References: [1] J. Bezombes, K. B. Borisenko, P. B. Hitchcock, M. F. Lappert, J. E. Nycz, D. W. H. Rankin, H. E.Robertson, J. Chem. Soc. Dalton Trans., 2004, 1980. [2] M. J. S. Gynane, A. Hudson, M. F. Lappert, P. P. Power, H. Goldwhite, J. Chem. Soc., Dalton Trans., Inorg.Chem. 1980, 12, 2428. [3] N. A. Giffin, A. D. Hendsbee, T. L. Roemmele, M. D. Lumsden, C. C. Pye, J. D. Masuda, Inorg. Chem.,2012, 51, 11837. [4] J. Bezombes, P. B. Hitchcock, M. F. Lappert, J. E. Nycz, Dalton Trans., 2004, 499. [ ] D. Förster, „Zur PP-Bindungsreaktivität in unsymmetrischen und symmetrischen Nheterozyklischen Diphosphanen“, Dissertation, 2013. [6] D. Förster, H. Dilger, F. Ehret, M. Nieger, D. Gudat, Eur. J. Inorg. Chem., 2012, 3989.

Poster presentation - P091

Synthesis of P-functional thiazole-2-thiones – precursors for NHCs? Imtiaz Begum, Rainer Streubel* [email protected] Institut für Anorganische Chemie, Rheinische Friedrich-Wilhelms Universität Bonn, Gerhard Domagk-str.1, 53121 Bonn, Germany Thiazole-2-thiones and their derivatives have tremendous potential in various fields, including their medicinal and biological activities.[1] Similar to P-substituted imidazole-2-thiones[2] they also represent interesting precursors for NHCs and, hence, can be considered as versatile ligands in metal coordination chemistry.[3] Herein, we present the synthesis of novel C-phosphanyl 2, C-phosphanoyl 3 and mixed substituted thiazole-2-thiones 4/5 starting from 1 (Scheme). Compound 2 was converted into the P-functional thiazolium salt 6, and via deprotonation and in situ reaction with [Rh(cod)Cl]2 into the thiazol-2-ylidene rhodium(I) complex 7.[4] Currently, studies on the synthesis of precursors of bis-NHCs having one (or two) phosphorus unit as linker as well as on their reactivities are underway.

Acknowledgements: We are grateful to the DAAD for financial support PhD fellowship for I. Begum References: [1] D. Havrylyuka, L. Mosulaa, B. Zimenkovskya O. Vasylenkoc, A. Gzella , R. Lesyka, Eur. J. Med. Chem. (2010), 45, 5012-5021. [2] P. K. Majhi, S. Sauerbrey, A. Leiendecker, G. Schnakenburg, A. J. Arduengo III, R. Streubel, Dalton Trans. 2013, 42, 13126-13136. [3] A. J. Arduengo III, J. R. Goerlich, W. J. Marshall, Liebigs Ann./recueil, 1997, 365-374. [4] R. Streubel, I. Begum, G. Schnakenburg, to be submitted.

Poster presentation - P092

Exploring the accessibility of thiaphosphirane complexes anew J. Fassbender, R. Streubel* [email protected] Institut für Anorganische Chemie der Rheinischen Friedrich-Wilhelms-Universität Bonn Gerhardt-Domagk-Str. 1, GER-53121 Bonn While oxaphosphirane complexes[1] have received considerable interest in the last years, only very little is known about their sulfur analogues, namely thiaphosphirane complexes.[2] We will present the results of our attempts to synthesize thiaphosphirane complexes III via the reaction of Li/Cl phosphinidenoid complexes I[3] with C-S πsystems, following our most recent successful[3] synthetic protocol for oxaphosphirane complexes. Additionally, DFT studies[4] on the reaction pathways that lead to the observed products 1, 2 as well as possible intermediates, such as the zwitterionic complex II or the thiaphosphirane complex III, will be discussed. Furthermore, NMR and X-ray structural data of 1 and 2 will be provided.

Acknowledgements: This work was financially supported by the DFG (STR 411/26-3), and it is dedicated to Prof. F. Mathey. References: [1] (a) S. Bauer, A. Marinetti, L. Ricard, F. Mathey, Angew. Chem. Int. Ed. Engl., 1990, 29, 1166– 1167; (b) R. Streubel, A. Kusenberg, J. Jeske, P. G. Jones, Angew. Chem. Int. Ed. Engl., 1994, 33, 2427–2428. [2] (a) E. Niecke, H.-J. Metternich, M. Nieger, D. Gudat, P. Wenderoth, W. Malisch, C. Hahner, W.Reich, Chem. Ber., 1993, 126, 1299 – 1309; (b) R. Streubel, C. Neumann, J. Chem. Soc., Chem. Commun., 1999, 499–500; (c) S. Maurer, T. Jikyo, G. Maas, Eur. J. Org. Chem., 2009, 2195–2207. [3] (a) A. Özbolat, G. von Frantzius, J. Marinas Pérez, M. Nieger, R. Streubel, Angew. Chem. Intl. Ed. Engl., 2007, 46, 9327 – 9330; (b) V. Nesterov, G. Schnakenburg, A. Espinosa, R. Streubel, Inorg. Chem., 2012, 51, 12343–12349. [4] R. Streubel, J. Faßbender, G. Schnakenburg, A. Espinosa Ferao, Chem. Comm., 2015, submitted.

Poster presentation - P093

1,3,5-Triphosphabenzenes: Molecules with a Thirst for Hydrogen Rosalyn L. Falconer*, Christopher A. Russell, Douglas W. Stephan [email protected] School of Chemistry, University of Bristol CantockÄs Close, Bristol, BS8 1TS, UK The development of main group compounds that mimic the chemistry of transition metals is an emerging theme in modern research.[1] Recent publications have highlighted unexpected aspects of the reactivity of 1,3,5-triphosphabenzenes which display pronounced transition metal-like characteristics.[2] For example, 2,4,6-tri-tertbutyl-1,3,5-triphosphabenzene reacts with hydrogen under mild conditions; remarkably, the initial addition was shown to be reversible.[3] Furthermore, alkenes have been shown to bind reversibly across the 1,4-sites of this heteroaromatic substrate.[4] Clearly this significantly resembles transition metal chemistry and paves the way for new research into the area. We have expanded investigations of the reactivity of 1,3,5-triphosphabenzenes by studying their reactivity with other small molecules. Across a range of chemically very different molecules (e.g., germanes, silanes, dienes), 1,3,5-triphosphabenzenes demonstrate a remarkable ability to abstract hydrogen from this diverse range of substrates. In this presentation, this remarkable “thirst for hydrogen” will be explored.

Figure 1. Reversible reactivity of 1,3,5-triphosphabenzenes with hydrogen and alkenes.

References: [1] P. P. Power, Nature 2010, 463, 171-177. [2] R. L. Falconer, C. A. Russell, Coord. Chem. Rev., 2015, in the press, DOI: 10.1016/j.ccr.2015.02.010 [3] L. E. Longobardi, C. A. Russell, M. Green, N. S. Townsend, K. Wang, A. J. Holmes, S. B. Duckett, J. E. McGrady, D. W. Stephan, J. Am. Chem. Soc., 2014, 38, 13453–13457. [4] C. Peters, H. Disteldorf, E. Fuchs, S. Werner, S. Stutzmann, J. Bruckmann, C. Krüger, P. Binger, H. Heydt and M. Regitz, Eur. J. Org. Chem., 2001, 18, 3425–3435.

Poster presentation - P094

[ClP(µ-PMes*)]2 – A Versatile Reagent in Phosphorus Chemistry Jonas Bresien, Axel Schulz,* Alexander Villinger [email protected] Department of Chemistry, University of Rostock Albert-Einstein-Straße 3a, D-18059, Rostock Ring systems composed of group 15 elements (pnictogens, Pn) are an interesting and widely investigated field of main group chemistry.[1,2] Following our group’s specific interest in halogen substituted cyclo-phosphanes, we started to investigate the reactivity of dichloro-cyclo-tetraphosphane [ClP(µ-PMes*)]2 (1), whose synthesis was recently reported.[3] Treatment of 1 with Lewis acids led to the formation of an unprecedented bicyclic triphosphino-phosphonium ion, [Mes*P4(Cl)Mes*]+ (2+, Figure 1).[4] In case of GaCl3, the formation of 2+ occured via a highly reactive tetraphosphenium cation (3+), whereas use of Ag[WCA] (WCA = weakly coordinating anion) gave rise to an intermediate dinuclear silver complex (42+). In the presence of suitable Lewis bases, substitution of the Cl atoms was accomplished. Depending on the sterical demand of the Lewis base, the substitution products can either be four membered ring systems (5, 6) or diphosphene species (7) as the result of a formal [2+2] cycloreversion reaction. Reduction of 1 with metals yielded neutral tetraphosphabicyclobutane Mes*P4Mes* (8) or anionic triphosphenide [Mes*P3Mes*] (9 ), depending on the stoichiometry.

Figure 1. Product scope accessible through cyclo-tetraphosphane 1 (R = C or Pn based group).

References: [1] M. S. Balakrishna, D. J. Eisler, T. Chivers, Chem. Soc. Rev. 2007, 36, 650–664. [2] G. He, O. Shynkaruk, M. W. Lui, E. Rivard, Chem. Rev. 2014, 114, 7815–7880. [3] J. Bresien, C. Hering, A. Schulz, A. Villinger, Chem. Eur. J. 2014, 20, 12607–12615. [4] J. Bresien, K. Faust, A. Schulz, A. Villinger, Angew. Chem. Int. Ed. 10.1002/anie.201500892.

2015,

Poster presentation - P095

Binary, Protonated Seven-Atom Zintl Anions [H2GeP6]2– and [H2SiP6]2– Lukas Guggolz, Stefan Mitzinger, and Stefanie Dehnen* [email protected] Department of Chemistry Philipps-Universität Marburg Hans-Meerwein-Str. 4 35043 Marburg In the course of our recent studies of group 14/15 Zintl anions as precursors for the formation of ternary M/14/15 intermetalloid clusters,[1-4] two compounds comprising Zintl anions that are based on the seven-atom species [GeP6]n- and [SiP6]n- were synthesized and characterized by means of X-ray diffraction studies, mass spectrometry, and 31P-NMR spectroscopy. The studies confirm the presence of two [K([2.2.2]crypt)]+ counterions, which is in disagreement with the pseudo-element concept that would accord with a 4– charge of the nortricyclan-type cages of the given composition. For this, density functional theory (DFT) studies were applied that served to suggest a doubly-protonated nature of the species, to determine the most stable charge distribution as well as the most probable position of the respective group 14 element and the protons. Simultaneous optimizations of the geometric and the electronic structure were therefore undertaken for naked clusters charged 2– and 4–, as well as for the protonated derivatives [H2GeP6]2– and [H2SiP6]2–. In parallel, we perform systematic studies on tetrahedral group 13/14, 13/15, and 14/15 binary Zintl anions regarding their stability and reactivity towards organic functionalization.

Figure 1. Structure and composition of the most stable isomers of [GeP6]4– (left) and [H2GeP6]2– (right). References: [1] F. Lips, R. Clérac, S. Dehnen, Angew. Chem. 2011, 123, 986–990; Angew. Chem. Int. Ed. 2011, 50, 955–959. [2] F. Lips, S. Dehnen, Angew. Chem. 2011, 123, 991–995; Angew. Chem. Int. Ed. 2011, 50, 960–964. [3] R. Ababei, W. Massa, K. Harms, X. Xie, F. Weigend, S. Dehnen, Angew. Chem. 2013, 125, 13786– 13790; Angew. Chem. Int. Ed. 2013, 52, 13544–13548. [4] S. Mitzinger, L. Broeckaert, W. Massa, F. Weigend, S. Dehnen, Chem. Comm. 2015, 51, 3866– 3869.

Poster presentation - P096

Functionalization of P4 using Lewis acid-stabilized bicyclo[1.1.0]tetraphosphabutane anions Jaap E. Borger, Andreas W. Ehlers, Martin Lutz, J. Chris Slootweg and Koop Lammertsma* [email protected] Department of Chemistry and Pharmaceutical Sciences VU University Amsterdam, De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands The direct incorporation of white phosphorus into organic fragments is a challenge and represents an important target in organophosphorus chemistry.[1] The high reactivity makes white phosphorus unpredictable. To allow selective conversions, control is required.[2] A novel approach is the use of organolithium reagents. These carbon-centered nucleophiles can open up the P4 cage and form P-C bonds. However, these highly reactive reagents often give low selectivity and complex product mixtures.[3, 4] The first step is believed to be the scission of one of the P-P bonds in the P4‑tetrahedron to generate an anionic, butterfly-like bicyclotetraphosphabutane moiety.[4b, 5] Thus far, such intermediates have not been isolated. Yet, their selective formation is of interest as the first step in controlling the selective formation of P-C bonds from P4. On this poster, we describe the synthesis of anionic butterfly fragments by reacting sterically encumbered aryllithium and Lewis acids with P 4 and discuss their reactivity.[6]

Figure 1. Synthesis and reactivity of Lewis acid stabilized bicyclotetraphosphabutane anions. Acknowledgements: This work was supported by the Council for Chemical Sciences of the Netherlands Organization for Scientific Research (NWO/CW) References: [1] (a) C.C. Cummins et al., Chem. Rev., 2010, 110, 4164; (b) M. Peruzzini et al., Chem. Rev., 2010, 110, 4178; (c) M. Scheer et al., Chem. Rev., 2010, 110, 4236. [2] J.M. Lynam, Angew. Chem. Int. Ed., 2008, 47, 831. [3] E. Fluck et al., Angew. Chem. Int. Ed., 1985, 24, 1056. [4] (a) M.M. Rauhut et al., J. Org. Chem., 1963, 28, 471.; (b) J. Org. Chem., 1963, 28, 473. [5] (a) M. Baudler et al., Angew. Chem. Int. Ed., 1988, 27, 1059. (b) F. Knoll et al., Mh. Chem., 1966, 97, 808. [6] K. Lammertsma et al., Angew. Chem. Int. Ed., 2014, 53, 12836.

Poster presentation - P097

Fixation and liberation of intact E4 tetrahedra (E = P, As) Fabian Spitzer and Manfred Scheer* [email protected] Institute of Chemistry, University of Regensburg Universitätsstr. 31, 93053 Regensburg Complexes containing tetrahedral P4 ligands represent the first step of P4 activation.[1] Several neutral and cationic complexes with a P4 tetrahedron in η1 or η1:1 coordination mode are known.[2] However, only few edge coordinated P4 complexes are reported, so far.[3] Hereby two extreme cases are to be distinguished: Either electrons are transferred to the P4 moiety or the P4 tetrahedron stays intact. For a reliable classification computational methods are needed. A neutral complex bearing a η2- or η2:2-coordinated P4 ligand with intact edges is still missing. Neutral examples for the heavy analogue, yellow arsenic, are so far unknown. We present the complexes [(LCu)2(μ,η2:2-E4)] (E = P (1a), As (1b), L = [{N(C6H3iPr22,6)C(Me)}2CH]-) containing intact E4 tetrahedra as bridging ligands. Furthermore, we report on the formation of the mononuclear complex [ Cu(η2-P4)] (2) as the first neutral molecule bearing an intact η2-P4 ligand. The integrity of all coordinated tetrahedra was confirmed by DFT calculations. To prove this theoretical prediction, the E4 ligands were substituted with the stronger Lewis-base pyridine. The released white phosphorus and yellow arsenic could be monitored by 31P{1H} and 75As{1H} NMR spectroscopy, respectively.

References: [1] a) B. M. Cossairt, N. A. Piro, C. C. Cummins, Chem. Rev. 2010, 110, 4164-4177; b) M. Caporali, L. Gonsalvi, A. Rossin, M. Peruzzini, Chem. Rev. 2010, 110, 17 - 23 c) M. Scheer, G. Balázs, A. Seitz, Chem. Rev. 2010, 110, 4236-4256; d) S. Khan, S. S. Sen, H. W. Roesky, Chem. Commun. 2012, 48, 2169-2179; e) N. A. Giffin, J. D. Masuda, Coord. Chem. Rev. 2011, 255, 1342-1359. [2] a) S. Heinl, E. V. Peresypkina, A. Y. Timoshkin, P. Mastrorilli, V. Gallo, M. Scheer, Angew. Chem. Int. Ed. 2013, 52, 10887-10891; b) T. Gröer, G. Baum, M. Scheer, Organometallics 1998, 17, 59165919; c) V. Mirabello, M. Caporali, V. Gallo, L. Gonsalvi, D. Gudat, W. Frey, A. Ienco, M. Latronico, P. Mastrorilli, M. Peruzzini, Chem. Eur. J. 2012, 18, 11238-11250. [3] a) I. Krossing, L. van Wüllen, Chem. Eur. J. 2002, 8, 700-711; b) G. Santiso-Quinones, A. Reisinger, J. Slattery, I. Krossing, Chem. Commun. 2007, 5046-5048; c) L. C. Forfar, T. J. Clark, M. Green, S. M. Mansell, C. A. Russell, R. A. Sanguramath, J. M. Slattery, Chem. Commun. 2012, 48, 1970-1972.

Poster presentation - P098

Functionalization of [Cpʹʹ2Zr(1:1-P4)] Andreas E. Seitz, Manfred Scheer* [email protected] Institute of Inorganic Chemistry, University of Regensburg, Universitätsstraße 31, GER-93053, Regensburg In the past few years, the activation and functionalization of white phosphorus as well as the transfer of phosphorus units became a central area of research in the field of Inorganic Chemistry.[1] A reasonable approach to study the stepwise degradation of P4 is the functionalization of P4 butterfly complexes. Herein, we report on the reaction of [Cpʹʹ2Zr(1:1-P4)] with tert-Butyllithium at low temperature and subsequent reactions.

References: [1] Recent Reviews on P4 activation: a) B. M. Cossairt, N. A. Piro, C. C. Cummins, Chem. Rev. 2010, 110, 4164-4177; b) M. Caporali, L. Gonsalvi, A. Rossin, M. Peruzzini, Chem. Rev. 2010, 110, 41784235; c) M. Scheer, G. Balázs, A. Seitz, Chem. Rev. 2010, 110, 4236-4256.

Poster presentation - P099

Synthesis and Application of Weighable Brønsted Acids Containing Hexacoordinated Phosphorus(V) Anions K. Hazin, P.W. Siu, D.P. Gates* [email protected] Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, BC, Canada V6T 1Z1 The development of solid, weighable Brønsted acids is of particular interest due to their potential use in bond activation reactions.1 However, systems of the type H+[X]are not generally isolable due to the inherent high reactivity of most anions with H +. The bonding nature of weakly coordinating anions (WCA) facilitates the successful isolation of Brønsted acids and plays a critical role in the generation and stabilization of highly reactive cations. Our research focuses on employing the known charge balancing tris(tetrachlorobenzenediolato)phosphate anion (TRISPHAT, [1]-)2 to afford a novel class of isolable Brønsted acids. The synthesis and characterization of the solid, weighable HL2[1] (Figure 1, L = donor solvent) will be discussed.3 In addition, the application of HL2[1] as an effective single-component initiator for the carbocationic polymerization of vinyl monomers at a variety of temperatures and monomer-to-initiator ratios will be surveyed.

Figure 1. Cationic olefin polymerization with hexacoordinated phosphorus(V) anion.

References: [1] (a) R.J. Phipps, G.L. Hamilton, F.D. Toste, Nature Chemistry 2012, 4, 603-614; (b) I. Krossing, I. Raabe, Angew. Chem. Int. Ed. Engl. 2004, 43, 2066-2090. [2] J. Lacour, C. Ginglinger, C. Grivet, G. Bernardinelli, Angew. Chem. Int. Ed. Engl. 1997, 36, 608610. [3] (a) P.W. Siu, K. Hazin, D.P. Gates, Chem. Eur. J. 2013, 27, 9005-9014; (b) P.W. Siu, D.P. Gates, Can. J.Chem. 2012, 90, 574-583; (c) P. W. Siu, D.P. Gates, Organometallics 2009, 28, 4491-4499.

Poster presentation – P100

N-Trimethylsilylsulfinylamine - Reactivity and Isomerisation Induced by Lewis Acids René Labbow, Axel Schulz,* and Alexander Villinger [email protected] Department of Chemistry, University of Rostock Albert-Einstein-Straße 3a, D-18059 Rostock Sulfinylimine HNSO was probably first discovered by F. Ephraim and H. Piotrowski in 1911.[1,2] Its low boiling point below –60°C renders this compound impractical for applied chemistry. Substitution of the proton against a Me3Si group led to the title compound.[3,4] We will report of Lewis acid assisted isomerisation of this sulfinylamine to a siloxathiazate 1 (Figure 1 right). Our investigations refer to the reaction presented in Figure 1 using different classical Lewis acids like gallium trichloride GaCl3or the more sterically demanding borane B(C6F5)3as well as highly reactive species like the trimethylsilyl cation [Me3Si]+. In this manner, different Lewis acids led on different pathways to the formation of adducts (pathway A), adducts of the isomeric sulfanylidyneamine -OSN (pathway B) or a homoleptic cation (pathway C). These precursors can be used to build up heterocyclic compounds containing sulfur, nitrogen and oxygen or any combination of these elements.[5]

Figure 1: Left: reaction pathways, right: molecular structure of 1.

References: [1] F. Ephraim, H. Piotrowski, Chem. Ber. 1911, 44, 379–386. [2] P. W. Schenk, Chem. Ber. 1942, 75, 94–99. [3] O. J. Scherer, P. Hornig, Angew. Chem. Int. Ed. 1966, 5, 729–730. [4] K. I. Gobbato, C. O. Della Védova, H. Oberhammer, J. Mol. Struct. 1995, 350, 227–231. [5] S. I. Bell, M. Parvez, S. M. Weinreb, J. Org. Chem. 1991, 56, 373–377.

Poster presentation – X101

Synthesis and Reactivity of a Triflyloxyphosphonium Dication Sivathmeehan Yogendra,(a) Felix Hennersdorf,(a) Antonio Frontera,(b) Roland Fischer(c) and Jan J. Weigand(a)* [email protected] Department of Chemistry and Food Chemistry (a) Department of Chemistry and Food Chemistry, TU Dresden, Mommsenstrasse 4, GER-01162, Dresden (b) Departament of Chemistry, Universitat de les Illes Balears (c) Department of Inorganic Chemistry, TU Graz N-heterocyclic carbenes (NHCs)[1] and cyclopropenylidenes (CPDs)[2] have been proven to be powerful ligands facilitating the stabilization of highly reactive, cationic P-derivatives. In this context, carbodiphosphoranes (CDPs) are an interesting class of ligands due to their expected enhanced stabilization effects as the result of their additional π-donor properties. This was recently demonstrated by the use of (Ph3P)2C as a valuable ligand in the synthesis of a low-coordinated P(III)-dication.[3] Therefore, we are currently investigating (Ph3P)2C as a suitable ligand for the synthesis of electron deficient phosphonium salts. The two step reaction of 1[OTf] with i) tBuO2H and ii) Tf2O affords the triflyloxyphosphonium dication 2+ as triflate salt in high yield. The presence of the (Ph3P)2C-substituent renders an unusual reactivity of compound 2[OTf]2 by featuring two electrophilic reaction sides. As an example, heating 2[OTf]2 at elevated temperature (~ 200 °C) leads to the elimination of HOTf accompanied with the formation of 3[OTf]2. Further unusual transformation reactions are presented in this poster.

References: [1] (a) M. H. Holthausen, M. Mehta, D. W. Stephan, Angew. Chem. Int. Ed. 2014, 53, 6538;(b) K. Schwedtmann, M. H. Holthausen, K.-O. Feldmann, J. J. Weigand, Angew. Chem. Int. Ed. 2013, 125, 14204; (c) J. J. Weigand, K.-O. Feldmann, F. D. Henne, J. Am. Chem. Soc. 2010, 132, 16321. [2] (a) J. Petuŝkova, M. Patil, S. Holle, C. W. ehmann, W. Thiel, M. Alcarazo, J. Am. Chem. Soc. 2011, 133, 20758. [3] M. Q. Y. Tay, Y. Lu, R. Ganguly, D. Vidović, Angew. Chem. Int. Ed. 2013, 52, 3132.

Poster presentation – X102

Synthesis and Structure of Terdentate Ketoiminate Complexes Roman Olejník, Zdeňka Růžičková, Jan Merna, Aleš Růžička [email protected] University of Pardubice, Faculty of Chemical Technology, Department of General and Inorganic Chemistry Studentská 573, CZ-532 10 Pardubice, CzechRepublic The coordination chemistry of the group 12-14 elements has attracted a significant interest in particular due to remarkable reactivity and possible wide range of applications starting from organic transformations[1] to various polymerizations reactions[2]. Terdentate ketoiminate may be classified among the most widespread spectator systems which can stabilize metal centers and thus form six membered metallacycles. The central fragment consists of NC3O skeleton and renders space for variation a number of its substituents or could by formally a part of hetero/aromatic rings and also nitrogen atom could be substituted by different entities with tunable steric demand and character. The preparation of target complexes can be classified into two main reaction procedures. The first one is transmetallation of deprotonated ketoimine species with metal halogenide MCl2(M = Sn(II), Ge(II) and Zn(II)). The other pathway is protolithic reaction of a pro-ligand and an appropriate reactive compound such as metal bisamide (M[N(TMS)2]2, M(II) = Ge, Sn) or metal alkyls (MR n , M = Zn(II), Al(III); R = Me, Et), which produced desired products via an amine or alkyl elimination route. Obtained complexes (Figure 1) were used for further tests of its reactivity or as co-initiators for co/polymerization reactions (εcaprolactone, trimethylene carbonate etc.). Comprehensive study of tetrylene complexes is supported by quantum chemistry calculations.

Figure 1. The molecular structure of one of the compounds studied.

Acknowledgements: We gratefully acknowledged the financial support of the Czech Science Foundation (project no. P207/11/0705). References: [1] M. Asay, C. Jones, M. Driess,Chem. Rev., 2011, 111, 354-396. [2] N. M. Rezayee, K. A. Gerling, A. L. Rheingold, J. M. Fritsch, Dalton Trans., 2013, 42, 5573-5586.

Poster presentation - P103

A Novel Synthesis of the 2-Phosphaethynolate Anion and Subsequent Reactivity Andrew R. Jupp, Jose M. Goicoechea* [email protected] Department of Chemistry, University of Oxford 12 Mansfield Rd, Oxford, OX1 3TA, UK Expanding on previous research on the activation of [P7]3– by unsaturated molecules,[1] we report that the heptaphosphide trianion reacts with ambient pressures of carbon monoxide to form the phosphaethynolate anion, PCO–.[2] This phosphorus containing analogue of the ubiquitous cyanate anion has been the subject of a number of recent articles by our group and those of Grützmacher and Cummins.[3,4] We have systematically explored the ligand properties and cycloaddition chemistry of PCO– towards a range of heteroallenes, yielding several novel heterocycles.[2] Furthermore, by analogy with Wöhler’s paradigm-shifting synthesis of urea in 1828, the reaction of >PCO– with ammonium salts yields the unprecedented phosphinecarboxamide.[5] This inorganic analogue of urea is a rare example of an airstable primary phosphine, and its ligand properties have been explored.[6] We have also explored its Brønsted acidity to afford a series of novel phosphides, secondary and tertiary phosphines, and phosphine oxides.[7]

Figure 1. Formation of novel anionic P-containing heterocycles from PCO–.

Acknowledgements: We thank the University of Oxford and EPSRC for funding. References: [1] R. S. P. Turbervill, J. M. Goicoechea, Chem. Rev. 2014, 114, 10807. [2] A. R. Jupp, J. M. Goicoechea, Angew. Chem., Int. Ed. 2013. 52, 10064. [3] F. F. Puschmann, D. Stein, D. Heift, C. Hendriksen, Z. A. Gal, H.-F. Grützmacher, H. Grützmacher, Angew. Chem. Int. Ed. 2011, 50, 8420. [4] I. Krummenacher, C. C. Cummins, Polyhedron, 2012, 32, 10. [5] A. R. Jupp, J. M. Goicoechea, J. Am. Chem. Soc. 2013, 135, 19131. [6] M. B. Geeson, A. R. Jupp, J. E. McGrady, J. M. Goicoechea, Chem. Commun. 2014, 50, 12281. [7] A. R. Jupp, G. Trott, É. Payen de la Garanderie, J. D. G. Holl, D. Carmichael, J. M. Goicoechea, Chem. Eur. J. Manuscript accepted for publication

Poster presentation - P104

Pentaphospha- and Pentaarsaferrocene A Comparative Study of Their Coordination Ability Towards Weakly Coordinating Lewis Acids Martin Fleischmann, Manfred Scheer* [email protected] Institute of Inorganic Chemistry, University of Regensburg Universitätsstraße 31, GER-93053, Regensburg During the last decades supramolecular chemistry based on weak interactions like hydrogen bonds, van der Waals interactions or weak dative bonds instead of strong covalent bonds has gained more and more attention. In this context, we are investigating the coordination chemistry of heavier Group 15 element ligands. The discovery of the all-phosphorus and all-arsenic analogue of the well-known cyclopentadienyl ligand in [Cp*Fe(η5-E5)] (E = P, As) by Scherer et al. about twenty years ago can be viewed as a milestone in organometallic chemistry.[1] These complexes contain a subtituent-free planar E5 ring which enables them to act as ligands in coordination chemistry themselves. While the reaction of the cyclo-P5 complex with CuI halides leads to fullerene-like spherical supermolecules[2] and capsules,[3] similar reactions of the analogues cyclo-As5 complex result in polymeric compounds.[4] These investigations reveal a preferred π-coordination for As instead of a σ-coordination in the case of P. This poster presents the interaction of the Lewis acids Ag+ and Tl+ with the cyclo-E5 rings of pentaphospha- and pentaarsaferrocene. Selected examples show unprecedented bonding modes and enable a direct comparison of these complexes.

Figure 1. Different coordination of the cyclo-P5 and cyclo-As5 complexes towards Ag+.

References: [1] (a) O. Scherer, T. Brück, Angew. Chem. Int. Ed. 1987, 26, 59; Angew. Chem. 1987, 99, 59. (b) O. Scherer, C. Blath, G. Wolmershäuser, J. Organomet. Chem. 1990, 387, C21. [2] J. Bai, A. Virovets, M. Scheer, Science 2003, 300, 781. [3] S. Welsch, C. Gröger, M. Sierka, M. Scheer, Angew. Chem. Int. Ed. 2011, 50, 1435; Angew. Chem. 2011, 123, 1471. [4] H. Krauss, G. Balázs, M. Bodensteiner, M. Scheer, Chem. Sci. 2010, 1, 337.

Poster presentation - P105

Chemistry of Cationic Arsines: A New Class of Electrophilic Ligands Jonathan W. Dube, Manuel Alcarazo [email protected] Department of Organometallic Chemistry Max Planck Institut für Kohlenforschung, Kaiser-Wilhelm-Platz-1, DE-45470, Mülheim an der Ruhr Finely tuning the structure and design of ligands is a critical component to the development of new transition-metal mediated processes. While the synthesis of new phosphine and carbene compounds is an active area of investigation, the extension of ligand design to arsenic is relatively unexplored. This is despite the fact that arsines are known to be poorer σ–donors and π–acceptors when compared to phosphines, which could be useful for a number of catalytic reactions.1 In this context, this presentation will focus on our efforts in cationic arsine chemistry, as an extension of our interest in polycationic phosphines (ie. A-C).2 A novel arsenic proligand with a cationic cyclopropenium substituent (1) is prepared in high yields and is indefinitely air and moisture stable. Despite being highly electrophilic, 1 is capable of forming a number of bottleable transitional metal complexes, for example with gold (2), platinum, and palladium (3). This is contrary to conventional electron-poor arsines (ie. AsF3, As(C6F5)3), which do not coordinate to these elements. In addition to this remarkable coordination chemistry, the chemical oxidation with XeF2(4), preparation of other derivatives, and application in π–acidic catalysis will be discussed.

Figure 1. Structures of representative arsenic compounds to be described.

Acknowledgements: The authors are extremely grateful for the funding and excellent departments (NMR, X-ray, Mass) provided by the MPI. Financial support for this work was also provided by Max Planck Gesellschaft and the Deutsche Forschung Gemeinschaft. References: [1] (a) A. Fürstner, P. W. Davies, Angew. Chem. Int. Ed., 2007, 46, 3410; for an early example see (b) V. Farina, B. Krishnan, J. Am. Chem. Soc., 1991, 113, 9585. [2] M. Alcarazo, Chem. Eur. J., 2014, 26, 7868.

Poster presentation - P106

Reaction of the Lewis acid B(C6F5)3 with [Ph3SbO]2, Ph2P(O)OH and other Lewis bases containing oxygen acceptor atoms Ralf Kather, Enno Lork, Matthias Vogt, Jens Beckmann* [email protected] Institut für Anorganische Chemie Universität Bremen Leobener Str, GER-28359, Bremen The Lewis acid B(C6F5)3has found numerous applications as catalyst, e.g. for the homogenous olefin polymerization or the FLP activation of small molecules.[1,2] With triorganophosphine oxides, it has been also used to prepare archetypical Lewis pair complexes, such as Ph3POB(C6F5)3.[3] We have recently shown that the previously known dimeric (Ph3SbO)2can be disaggregated by B(C6F5)3giving rise to the formation of the analogous Ph3SbOB(C6F5)3(1) having a short bipolar single +Sb-OB– bond (see Figure).[4] The closely related reaction of B(C6F5)3with the weak Brønsted acid Ph2P(O)OH provided in situ the metastable acid HOPPh2OB(C6F5)3(2), the reactivity of which has been elaborated. In absence of other substrates it undergoes autoprotolysis affording eight-membered boraphosphinate ring [Ph2POB(C6F5)2O]2(3) and C6F5H (see Figure).[5] In the presence of the polymeric [Ph2SnO]nthe eight-membered Sn2P2O4 heterocycle [Ph2Sn(OPPh2O)2SnPh2] [HOB(C6F5)3]2(4) was formed.[5] In the reaction with Ph4Sn, phenyl group cleavage takes place and Ph3SnOPPh2O(B6F5)3(5) was obtained.

Figure 1. Molecular structures of Ph3SbOB(C6F5)3 (1), [Ph2POB(C6F5)2O]2 (3), and [Ph2Sn(OPPh2O)2SnPh2][HOB(C6F5)3]2 (4).

References: [1] W. E. Piers, T. Chivers, Chem. Soc. Rev., 1997, 26, 345. [2] D. W. Stephan, G. Erker, Angew. Chem. Int. Ed., 2010, 49, 46. [3] M. A. Beckett, D. S. Brassington, M. E. Light, M. B. Hursthouse, J. Chem. Soc., Dalton Trans., 2001, 11, 1768. [4] R. Kather, T. Svoboda, M. Wehrhahn, E. Rychagova, E. Lork. L. Dostal, S. Ketkov, J. Beckmann, Chem. Commun., 2015, 51, 5932. [5] R. Kather, E. Lork, E. Rychagova, S. Ketkov, J. Beckmann, Manuscript in preparation.

Poster presentation - P107

Polycyclic Amides with As and Sb L. Belter, W. Frank* [email protected] Institut für Anorganische Chemie und Strukturchemie, Lehrstuhl II: Material- und Strukturforschung, Heinrich Heine Universität Universitätsstraße 1, GER-40225, Düsseldorf Polycyclic and cage-like amides of As, Sb and Bi are still very rare, especially those containing more than one of these elements. The first polycyclic amide containing both the elements As and Sb (4) was synthesized in 1994 by M. Veith et al. via classical salt elimination reaction.[1] 4 as well as further compounds with different substitution patterns were now successfully synthesized by the reaction of diazarsasiletidines (1-3) with SbF3. Compounds 4-6 show an unusual 3+1coordination of the Sb atom including a secondary Sb···N interaction.

Figure 1. Synthesis and crystal structures of polycyclic amides of As and Sb (4-6).

References: [1] M. Veith, A. Rammo, M. Hans, Phosphorus, Sulfur Silicon Relat. Elem. 1994, 93, 197-200.

Poster presentation - P108

The reactivity of As4 towards transition metal complexes Monika Schmidt, Manfred Scheer* [email protected] Institute of Inorganic Chemistry, University of Regensburg Universitätsstraße 31, GER - 93053 Regensburg Over the last few years, the activation of white phosphorus or yellow arsenic is in focus of current chemistry. Here, not only the degradation of the E4 tetrahedron is observed, also reaggregation proceeds. In the case of white phosphorus, a wide variety of substituent free Pn ligand complexes has been synthesized.[1] In contrast, yellow arsenic is not easy to handle especially due to its sensitivity to light. Therefore, only few results of As4 activation with transition metal fragments are reported.[2] Most of these Asn ligand complexes are synthesized by cothermolysis reactions at high temperatures. Thereby, cyclopentadienyl containing carbonyl complexes are often used as starting materials. Herein we report on the activation of As4 with transition metals. Furthermore the sterically demanding cyclopentadienyl ligand CpBn (CpBn = pentabenzylcyclopentadienyl) is introduced in this chemistry in order to receive unprecedented structural motifs. We succeeded, for instance, in synthesizing [(CpBnMo)2(µ,η5:5:1:1-As10)] by cothermolysis of [CpBnMo(CO)2]2 with As4.

References: [1] a) B.M. Cossairt, N. A. Piro, C. C. Cummins, Chem. Rev. 2010, 110, 4164-4177. b) M. Caporali. L. Gonsalvi, A. Rossin, M. Peruzzini, Chem. Rev. 2010, 110, 4178-4235. c) M. Scheer, G. Balázs, A. Seitz, Chem. Rev. 2010, 110, 4236-4256. [2] a) O. J. Scherer, Angew. Chem. 1990, 102, 1137-1155. b) O. J. Scherer, Acc. Chem. Res 1999, 32, 751-762.

Poster presentation - P109

Stibinidine and Bismuthinidine as ligands for TM Iva Vránová , Zdeňka Růžičková, Milan Erben, Libor Dostál [email protected] Department of General and Inorganic Chemistry, University of Pardubice Studentská 95, CZE-53210, Pardubice TM complexes of sub(low)-valent p-block element compounds have attracted considerable attention not only because of their unique structures, but also in the regard to their synthetic potential in organometallic chemistry. Our group has recently succeeded in the synthesis and structural characterization of the first monomeric stibinidene and bismuthinidene stabilized by an effective coordination of the N,C,Npincer type ligand.[1] The main drawback of this investigation was both relatively complicated synthesis of the N,C,N-ligand precursor and low yields of these lowvalent products observed after reduction of trivalent precursors. For these reasons, we modified the ligand backbone and we obtain new monomeric stibinidenes and bismuthinidenes. These monovalent RE(I) (E = Sb, Bi) species contain two electron lone pairs available for TM coordination (Figure 1). In this work the reactivity of monovalent stibinidenes and bismuthinidenes with selected TM complexes will be presented.

Figure 1: Coordination coordination capability of titled stibinidenes and bismuthinidenes.

Acknowledgements: The authors thank the Grant agency of Czech Republic project no. P207/1506609S. References: [1] P. Simon, F. de Proft, R. Jambor, A. Ruzicka, L. Dostal, Angew. Chem. Int-Ed., 2010, 49, 54685471.

Poster presentation - P110

Using Supramolecular Interactions to shape new Halogenido Bismuthate Materials Johanna Heine [email protected] Fachbereich Chemie, Philipps-Universität Marburg Hans Meerwein Straße, 35043, Marburg Interest in main group metal halogenido metalates has recently surged with perovskite based materials as a new candidate for solar cells.[1] Yet, while this has generated a flurry of activity in the field of stannates and plumbates, the related bismuthates also hold great potential for new materials with useful properties such as ferroelectricity or photoluminescence.[2] It has been our goal to evolve the functionality of these materials by using cations capable of extended supramolecular interactions. Using alkali metal crown ether adducts, extended viologens or metalloviologenes as cationic building blocks, we have obtained a host of new halogenido bismuthate materials and studied their optical properties – from basic absorption and emission characteristics to their thermo- and photochroism.

Figure 1. Combined thermo- and photochromism in halogenido bismuthate materials.

References: [1] B. V. Lotsch, Angew. Chem. Int. Ed., 2014, 53, 635- 637. [2] (a) N. Leblanc, N. Mercier, L. Zorina, S. Simonov, P. Auban-Senzier, C. Pasquier, J. Am. Chem. Soc., 2011, 133, 14924-14927.; (b) G. Xu, G.-C. Guo, J.-S. Guo, S.-P. Guo, X.-M. Jiang, C. Yang, M.S. Wang, Z.-J. Zhang, Dalton Trans., 2010, 39, 8688-8692.

Poster presentation - P111

Syntheses of Binary Interpnictogenes and their Reactivity Benjamin Ringler, Carsten von Hänisch* [email protected] Department of Chemistry Philipps-Universität Marburg Hans-Meerwein-Straße 4 GER-35032, Marburg On the poster we present syntheses of novel stibano amines. Additionally we investigate the reactivity of di‑tbutylstibano amine towards AlEt3and InEt3to achieve stibane substituted N2Al2/N2In2four rings.[1],[2] We discovered an access to novel binary interpnictogenes by converting di‑tbutylstibano chloride with lithiated primary amines to yield a fully tbutyl substituted amino stibane 1 and an ipropyl analogous 2. Furthermore stibano amines 3 and 4 can be obtained by reaction with lithium amide under different conditions. A condensation from 4 to 3 is observed while ammonia is formed. Compound 4 and AlEt3/InEt3are converted to [tBu2SbN(H)AlEt2]25 and [tBu2SbN(H)InEt2]26. We obtained the first examples where a nitrogen atom is connected to both antimony and aluminium/indium. Besides that antimony substituted Al2N2/In2N2four rings are a novelty among the well-known Al2N2/In2N2ring systems.

Figure 1. Reaction of a chloro stibane with amides to form stibano amines 1-4 and molecular structures of 5 and 6.

Acknowledgements: DFG-Graduiertenkolleg “Funktionalisierung von Halbleitern“ References: [1] B. Ringler, Master‘s thesis, Marburg, 2014. [2] B. Ringler, C. von Hänisch, manuscript in preparation.

Poster presentation - P112

Investigating non-covalent interactions in crowded frameworks by 77 Se and 125Te solid-state NMR Paula Sanz Camacho, Fergus R. Knight, Kasun S. Athukorala Arachchige, Daniel Dawson, Alexandra M. Z. Slawin, Jonathan R. Yates, J. Derek Woollins, and Sharon E. Ashbrook. [email protected] EaStCHEM School of Chemistry, St Andrews School of Chemistry , University of St Andrews, Fife KY16 9ST UK Non-covalent interactions are not as well studied as strong covalent and ionic bonding, and are still the focus of some controversy. However, these interactions are important as they can affect thermodynamic stability, molecular geometry, crystal packing, reactivity etc... of the compounds in which they occur. Naphthalene and acenaphthenes systems provide good models to study this type of interaction, as two large heteroatoms are constrained in the peri-positions of a rigid organic backbone. In this situation, in order to stabilize the steric hindrance that occurs between the heavy atoms, a weak interaction and/or distortion of the geometry is observed.1 In this work, we investigate not just intramolecular interactions between mixed peri-substituted acenaphthenes, shown in solution and in the solid-state by 77Se and 125Te solid-state NMR2, but also an unusual intermolecular interaction that occurs between two molecules (novel chalcogen-phosphorus heterocycles) that are packed such as the SeP distance smaller than the van der Waals radii. 77Se, 125Te and 31P results will be shown, together with DFT calculations, to understand the origin of these interactions. Furthermore, analysis of many of the compounds reveals significant polymorphism, not observed in the original single crystal diffraction data. The nature of the polymorphism present is then confirmed by a combination of solid-state NMR experiments, high-throughput „robot-based“ crystallography of a number of single crystals and first-principles calculations.

Figure 1. SSNMR and crystal structures of the new Compounds. References: [1] Aschenbach, L. K.; Knight, F. R.; Randall, R. A. M.; Cordes, D. B.; Baggott, A.; Buhl, M.; Slawin, A. M. Z., Woollins, J. D. Dalton Trans. 2012, 41, 3141. [2] Stanford, M. W.; Knight, F. R.; Athukorala Arachchige, K. S.; Sanz Camacho, P.; Ashbrook, S. E.; Bühl, M.; Slawin, A. M. Z.; Woollins, J. D. Dalton Trans. 2014, 43, 6548.

Poster presentation - P113

Supramolecular Interactions of 1,2,5-Selenadiazole Derivatives Lucia M. Lee, I. Vargas-Baca* [email protected] Department of Chemistry & Chemical Biology, McMaster University, Hamilton 1280 Main St. W Hamilton, ON, Canada L8S 4M1 Recent literature denotes a remarkable surge of interest in supramolecular interactions mediated by heavy p-block elements, “halogen bonding” is just a prominent example. While the σ‑hole model emphasizes the electrostatic component, covalent (polarization) and dispersion contributions also play a significant role in this phenomenon. All these factors are strongest for the heaviest elements. Indeed, compounds of tellurium very frequently form strong intermolecular links[2]. However, the strength of their supramolecular bonds can be manipulated by adjusting the electron acceptor ability of selenium. This is most efficiently accomplished by attachment, either formal or actual, of a Lewis acid[4] to one of the nitrogen atoms. We will present an overview of our systematic investigations and application of this approach to induce selenadiazoles to engage in supramolecular interactions. It includes the synthesis and structural characterization of transition-metal coordination polymers

Figure 1. Supramolecular structures based on benzo-2,1,3-selenadiazole. Acknowledgements: The support of the NSERC Canada is gratefully acknowledged. Part of this work was made possible by the facilities of the Shared Hierarchical Academic Research Computing Network (SHARCNET: www.sharcnet.ca) and Compute/Calcul Canada. References: [1] (a) A. F. Cozzolino, P. J. W. Elder, I. Vargas Baca, Coord. Chem. Rev. 2011, 255, 1426–1438. (b) A.F. Cozzolino, I. Vargas Baca, J. Organomet. Chem. 2007, 692, 2654–2657. [2] A. F. Cozzolino, I. Vargas Baca, S. Mansour, A. H. Mahmoudkhani, J. Am. Chem. Soc. 2005, 127, 3184–3190. [3] (a) L. M. Lee, P. J. W. Elder, A. F. Cozzolino, Q. Yang, I. Vargas Baca, Main Group Chem. 2010, 9, 117–133. (b) Cozzolino, A. F.; Elder, P. J. W.; Lee, L. M.; Vargas Baca, I. Can. J. Chem. 2013, 91, 338–347. [4] (a) M. Risto, R. W. Reed, C. M. Robertson, R. Oilunkaniemi, R. S. Laitinen, R. T. Oakley, Chem. Commun. 2008, 3278–3280. (b) G. Berionni, B. Pégot, J. Marrot, CrystEngComm 2009. 11, 986. (c) J. L. Dutton, J. J. Tindale, M. C. Jennings, P. J. Ragogna, Chem. Commun. 2006, 2474–2476. [5] L. M. Lee, P. J. W. Elder, P. A. Dube, J. E. Greedan, H. A. Jenkins, J. F. Britten, I. Vargas Baca, CrystEngComm. 2013, 15, 7434–7437.

Poster presentation - P114

Exploring new anionic selenium based pincer ligands Bronte J. Charette, Jamie S. Ritch* [email protected] Department of Chemistry, The University of Winnipeg; University of Manitoba 599 Portage Ave., R3B 2G3, Winnipeg, Manitoba, Canada Parker Building, R3T 2N2, Winnipeg, Manitoba, Canada The focus of this work lies in the synthesis, characterization and coordination of a series of anionic pincer ligands that contain selenium. Selenium and tellurium are soft Lewis bases that exhibit strong electron donor properties, and in conjunction with the hard Lewis base, nitrogen, should exhibit diverse new coordination chemistry. There are numerous examples of pincer ligands with phosphorus, nitrogen and carbon as donor atoms, but few examples exist of selenium and tellurium containing pincer ligands.[1] Transition metal complexes of such ligands have shown the potential to outperform their sulfur and phosphorus analogues as catalysts in the Heck reaction.[2] Such improvements could include promoting catalytic activity in more cost efficient metal complexes based on iron and nickel, compared to costly palladium. This presentation will focus on the synthesis and characterization of a new Se-N-Se pincer ligand based on a known PNP analogue.[3] The attempted coordination chemistry of this complex with transition metals will also be discussed.

References: [1] Kumar, A.; Rao, G. K.; Saleem, F.; Singh, A. K. Dalton Trans. 2012, 41, 11949-11977.
 [2] Yao, Q.; Kinney, E.; Zheng, C. Org. Lett. 2004, 6, 2997-2999.
 [3] Fryzuk. M. D.; Inorg. Chem. 1982,21, 2134-2139.

Poster presentation - P115

Coordination and Reduction of 1,2,5-Telluradiazole Heterocycles Nikolay A. Pushkarevsky*, Denis S. Grigoriev, Nikolay A. Semenov, Sergey N. Konchenko, Jens Beckmann, Andrey V. Zibarev [email protected] Nikolaev Institute of Inorganic Chemistry SB RAS Akademika Lavrentieva str. 3, 630090 Novosibirsk, Russia Chemistry of 1,2,5-telluradiazoles is intensely studied in the last decade. Despite molecular similarities to their S- and Se-containing analogs, they are largely different from those in structural aspects and reactivity. In condensed state they tend to form [Te2N2] secondary bonding units which are preserved upon formation of chargetransfer complexes[1] and, partly, upon coordination of the Te atom. In the case of chelating ligands (e. g. diamines), coordination polymers containing mono- or dimeric tellurodiazole units are formed (Fig. 1). Another contrast feature is the reduction processes, where thiadiazoles are known to form stable radical anions (RA)[2]. Stable telluradiazolyl RA are not known to date, while action of common reducing agents often results in the formation of species, apparently not containing RA. We present the latest data on the coordination of different types of neutral ligands (amines, phosphines, carbenes) to the Te atom of telluradiazole ring. Reaction behavior of telluradiazole systems with some reducing agents, as well as possible reaction pathways are discussed.

Figure 1. Two products of coordination of dicyanotelluradiazole with TMEDA (left); scheme of reduction of benzotelluradiazole (right), with the product of partial decomposition.

Acknowledgements: The authors are grateful to the Russian Foundation for Basic Research (grant No. 13-03-01088) and to the Deutsche Forschungsgemeinschaft (project BE 3716/3-1) for financial support. References: [1] N. A. Pushkarevsky, A. V. Lonchakov, N. A. Semenov, E. Lork, L. I. Buravov, L. S. Konstantinova, G. T. Silber, N. Robertson, N. P. Gritsan, O. A. Rakitin, J. D. Woollins, E. B. Yagubskii, J. Beckmann, A. V. Zibarev, Synthetic Met.,2012, 162, 2267–2276. [2] N. A. Semenov, N. A. Pushkarevsky, E. A. Suturina, E. A. Chulanova, N. V. Kuratieva, A. S. Bogomyakov, I. G. Irtegova, N. V. Vasilieva, L. S. Konstantinova, N. P. Gritsan, O. A. Rakitin, V. O. Ovcharenko, S. N. Konchenko, A. V. Zibarev, Inorg. Chem., 2013, 52, 6654–6663.

Poster presentation - P116

Coordination Chemistry of Selenium- and Tellurium-Containing Pincer Ligands Bronte J. Charette, Irit Shoichet, Jamie S. Ritch* [email protected] Department of Chemistry, The University of Winnipeg 515 Portage Avenue, Winnipeg, Manitoba, R3B 2E9, Canada Selenium and tellurium have widespread applications in materials chemistry, for instance in photovoltaic[1] and thermoelectric[2] materials. Compared to the use of organophosphines, however, the use of organochalcogen groups in ligands for coordination chemistry and catalytic applications remains relatively unexplored. Recent studies have shown such systems show great promise for promoting carboncarbon bond forming reactions with high efficiency, even exceeding the performance of phosphine-based systems in some cases.[3] To expand the structural variety of known heavy chalcogen pincers and establish structure-activity relationships, we are pursuing several new ligand motifs. This presentation will outline the synthesis and dblock coordination chemistry of new pincer-type ligands (Figure 1) featuring amido or carbene donors, flanked by organoselenium or tellurium groups.

Figure 1: Se,C,Se and Se,N,Se pincer ligands.

Acknowledgements: Financial support from the University of Winnipeg is gratefully acknowledged. References: [1] R. W. Birkmire, B. E. McCandless, Curr. Opin. Solid State Mater. Sci., 2010, 14, 139-142. [2] B. Poudel, Q. Hao, Y. Ma, Y. C. Lan, A. Minnich, B. Yu, X. A. Yan, D. Z. Wang, A. Muto, D. Vashaee, X. Y. Chen, J. M. Liu, M. S. Dresselhaus, G. Chen, Z. F. Ren, Science, 2008, 320, 634-638. [3] A. Kumar, G. K. Rao, A. K. Singh, RSC Adv., 2012, 2, 12552-12574.

Poster presentation - P117

Novel reaction of 1,2,5-chalcogenadiazoles – coordination of anions by chalcogen atoms Nikolay A. Semenov* , Elizaveta A. Suturina, Nikolay A. Pushkarevsky, Anton.V. Lonchakov, Irina Yu. Bagryanskaya, Enno Lork, Nina P. Gritsan, Jens Beckmann, Andrey V. Zibarev [email protected] Institute of Organic Chemistry, Russian Academy of Science Lavrentiev Ave 9, 630090 Novosibirsk, Russia It was recently found that 3,4-dicyano-1,2,5-chalcogenadiazoles possessing heavier chalcogens 1 and 2 interact with certain anions (X–) to form stable anionic complexes, in which X– are coordinated by chalcogen atom of heterocycle.[1] This contribution covers synthetic, structural and thermodynamic aspects of this novel reaction. All prepared complexes are characterized by single-crystal X-ray diffraction, ESI-MS, electronic absorption spectroscopy, as well as analyzed by means of DFT calculations. In all studied cases interaction may be described as donor-acceptor one – chemical bond between initial components is formed via negative hyperconjugation, i.e. electron density transfer from lone-pair orbital of X– onto the virtual σ -orbital of the E-N bond of chalcogenadiazole. Thus, this reaction is potentially of a general character and new objects – heterocycles, including 1,2,5-thiadiazoles, and anions may be involved.

Figure 1. Interaction of 3,4-dicyano-1,2,5-chalcogendiazoles with anions (left). X-Ray structure of the salt [K(18-crown-6)]+[2-SPh]- (right).

Acknowledgements: The authors are grateful to the Russian Foundation for Basic Research (project 14-03-31653) and Deutsche Forschungsgemeinschaft (project BE 3716/3-1) for the financial support. References: [1] N. A. Semenov, A. V. Lonchakov, N. A. Pushkarevsky, E. A. Suturina, V. V. Korolev, E. Lork, V. G. Vasiliev, S. N. Konchenko, J. Beckmann, N. P. Gritsan, A. V. Zibarev, Organometallics 2014, 33, 4302-4314.

Poster presentation - P118

PCP-Bridged, Chalcogen-Centered Ligands: Coordination Chemistry and Redox Transformations Jari Konu,*(a) Ian S. Morgan,(a) Heikki M. Tuononen,(a) Tracey L. Roemmele,(b) René T. Boeré,(b) Tristram Chivers [email protected] (a) Department of Chemistry, University of Jyväskylä P.O.Box 35, FI-40014, Jyväskylä, Finland (b) Department of Chemistry and Biochemistry, University of Lethbridge (c) Department of Chemistry, University of Calgary, Calgary, AB, Canada T2N 1N4 The versatile coordination and redox behaviour of the multidentate, PCP-bridged ligands 1 and 2, as well as their carbon based reactivity, has been recently established through various examples from main group and transition metal compounds.[1] This family of chalcogen-centered ligands has now been expanded with trichalcogeno monoanion 3, which displays a four-coordinate central PCP-carbon atom in contrast to the three-coordinate carbon centers in dianions 1 and 2. In this contribution we will describe the coordination behaviour of the novel ligand 3 and the redox activity of the resulting complexes, for instance, through the first example of structurally characterized six- and four-coordinate isomers of a Ni(II) complex with the same ligand (in 4a and 4b).

Figure 1. PCP-bridged, chalcogen-centered ligands and structural isomerism in the homoleptic Nickel(II) complex.

Acknowledgements: Financial support from the University of Jyväskylä and the Natural Sciences and Engineering Council (Canada) is gratefully acknowledged. References: [1] (a) T. Chivers, J. Konu, R. Thirumoorthi, Dalton Trans., 2012, 41, 4283 (review); (b) J. Konu, T. Chivers, H. M. Tuononen, Chem. Eur. J., 2011, 17, 11844; (c) J. Konu, T. Chivers, H. M. Tuononen, Chem. Eur. J., 2010, 16, 12977.

Poster presentation - P119

Ferrocenyl Substituted 1,3-Dithiolanes via [3+2]-Cycloadditions of Thiocarbonyl S-Methanides with Ferrocenyl/Hetaryl Thioketones Grzegorz Mlostoń*, Róża Hamera [email protected] epartment of rganic & Applied Chemistry, University of Łódź Department of Organic & Applied Chemistry, University of Łódź, PL-91-403 Łódź, Tamka 12, Poland Thioketones form a group of reactive dieno- and dipolarophiles, which are considered as versatile building blocks, useful for the preparation of sulfur heterocycles with variable ring size.[1] Ferrocenyl substituted sulfur heterocycles are of great importance.[2] Although the synthesis of diferrocenyl thioketone[3] was reported some time ago, the non-symmetrical, ferrocenyl functionalized thioketones are unknown. In our hands, thionation of ferrocenyl/hetaryl ketones using Lawesson’s Reagent opens a straightforward access to synthetically attractive ferrocenyl/hetaryl thioketones 1. In the course of our ongoing studies on the reactions of the C=S compounds with thiocarbonyl ylides 2, reactions of selected tioketones 1 with the in situ generated thiocarbonyl S-methanides were performed in THF solution. The 1H and 13C NMR analyses of crude reaction mixtures proved that the reactions occurred regioselectively and led to sterically crowded 1,3-dithiolanes 4 as sole or major products. In communication, the stepwise mechanism of a diradical [3+2]-cycloaddition via mesomeric stabilized 1,5-diradical 3 as a key intermediate,[4] will be discussed.

Acknowledgements: The authors thank the National Science Center (Cracow, Poland) for financial support within the grant Maestro (Grant Maestro-3 (Dec-2012/06/A/ST5/00219) References: [1] G. Mlostoń, H. Heimgartner, H. In Targets in Heterocyclic Systems, 10, Attanasi, O. A.; Spinelli, D. (Eds.); Società Chimica Italiana: Roma, 2006; 266–300. [2] . owalski, R. arpowicz, G. Mlostoń, D. Miesel, A. Hildebrandt, H. ang, R. Czerwoniec, B. Therrien, Dalton Transactions, 2015, 44, 6268. [3] M. Sato, M. Asai, J. Organomet. Chem. 1992, 430, 105. [ ] G. Mlostoń, P. Pipiak. A. Linden, H. Heimgartner, Helv. Chim. Acta, 2015, 98, DOI: 10.1002/hlca.201500057

Poster presentation - P120

Synthesis and biological evaluation of new 5-aryl-4,5-dihydro-1,3,4thiadiazole analogues as small molecule antimicrobial agents Mansura Akter, Rainer Streubel [email protected] Institut für Anorganische Chemie, Rheinische Friedrich-Wilhelms-Universität Bonn Gerhardt-Domagk-Str. 1, GER-53121 Bonn Aryl-1,3,4-thiadiazoles compounds have received considerable interest in the last years due to having their broad spectrum of biological activity.[1,2] The synthesis of a series of new 5-aryl-4,5-dihydro-1,3,4-thiadiazole analogues were carried out according to the procedure[3] described in figure 1. In the first step, the intermediate aryli-denethiosemicarbazone analogues 1-10 were prepared via condensation reaction of thiosemicarbazide and benzaldehyde derivatives in ethanol; upon cyclization with acetic anhydride 2,4-diacylated 5-aryl-1,3,4-thiadiazole analogues 11-20 were obtained.[4] The structures of the synthesized compounds were elucidated by using IR, 1 H NMR spectroscopic and mass spectrometric data. The antibacterial activities of the synthesized thiadiazole analogues were determined and most of the synthesized compounds showed notable antibacterial activities against both the Gram-positive and Gram-negative bacteria.

Figure 1: Synthesis of 5-phenyl- 4, 5-dihydro-1,3,4-thiadiazole analogues.

References: [1] Alam M. S., Liu L., Lee D. U., Chem. Pharm. Bull., 2011, 59, 1413. [2] a) Demirbas A., Sahin D., Demirbas N., Karaoglu S. A., Eur. J. Med. Chem., 2009,44, 2896—2903. b) Kumar D., Maruthi Kumar N., Chang K.-H., Shah K., Eur. J. Med. Chem., 2010,45, 4664—4668. c) Michael R., Stillings M. R., Welbourn A. P., Walter D. S., J. Med. Chem.,1986, 29, 2280—2284. [3] Kubota S., Ueda Y., Fujikane K., Toyooka F., Shibuya M., J. Org. Chem.,1980, 45, 1473—1477. [4] Akter M., Alam M. S., to be published.

Poster presentation - P121

In Search of Heavy Chalcogenido-d10-metallates Carsten Donsbach, Stefanie Dehnen* [email protected] Department of Chemistry, Philipps-University of Marburg Hans-Meerwein-Strasse 4, D-35032 Marburg Chalcogenidometallate compounds provide a variety in both structural and chemical properties while accessible via different synthetic pathways. Those include solid state as well as solvothermal and solution reactions. Solvothermal methods have been extended to the use of ionic liquids as solvent. Due to the interesting dissolving characteristics of ionic liquids (de-)construction and transformation of chalcogenidotetrelate frameworks are achieved by ionothermal treatment of binary precursors controlled by variation of solvent, temperature and additives.[1] Research in the field of semiconductor materials is also interested in heavy chalcogenidometallates and their photoelectrical and thermoelectrical properties. Synthesis via solid state and aminothermal reactions lead to potential precursor compounds for ionothermal treatment such as K2Hg3Se4, K2Hg2Se3 and K4PbSe4∙en∙NH3.[2] Current investigations are expanded from chalcogenidomercurates towards –thallates, –plumbates and –bismutates, using new ionic liquids.

Figure 1. Synthetic strategy towards chalcogenidometallate compounds. Acknowledgements: This work is supported by Deutsche Forschungsgemeinschaft (DFG) within the framework of SPP 1708. References: [1] Y. Lin, D. Xie, W. Massa, L. Mayrhofer, S. Lippert, B. Evers, A. Chernikov, M. Koch, S. Dehnen, Chem. Eur. J. 2013, 19, 8806-8813. [2] (a) M. G. Kanatzidis, Y. Park, Chem. Mat. 1990, 2, 99-101. (b) G. Thiele, S. Lippert, F. Fahrnbauer, P. Bron, O. Oeckler, A. Rahimi-Iman, M. Koch, B. Roling, S. Dehnen, 2015, submitted. (c) G. Thiele, T. Krüger, S. Dehnen, Angew. Chem. 2014, 126, 4787-4791.

Poster presentation - P122

Ionothermal Treatment of Chalcogenidometallates Silke Santner, Stefanie Dehnen* [email protected] Department of Chemistry, Philipps-Universität Marburg Hans-Meerwein-Strasse 4, D-35032 Marburg Open-framework chalcogenidotetrelates combine the advantages of zeolite-like structures with the physical and chemical properties of chalcogenides. Besides their formation in protic solvents, or by hydrothermal/solvothermal approaches, ionothermal reactions have recently received increasing attention.[1] In a bottom-up strategy, ionothermal reactions of binary or ternary precursors, such as [TSe4]4–, [T4Se10]4– (T = Ge, Sn) or [M4Sn4Se17]10– (M = Mn, Zn, Cd), with or without additional metal salts or amines were carried out. This yielded frameworks like 3D{[Sn9Se20]4–}[2] (1), the layered anionic structure 2D-{[Sn3Se7]2-}[3] (2), stabilized by in-situ formed [Mn(en)2.5(en-Me0)0.5]2+ ions,[4] or the molecular „zeoball“ anion [Sn36Ge24Se132]24–[5] (3) with spherical shape and a large cavity, being the largest main group element cluster anion known to date. By extending these synthetic strategies to further ionic liquid combinations or elemental compositions, including other metals as well as other chalcogenides, new interesting structures and properties are expected.

Figure 1. Ionothermal treatment of binary and ternary chalcogenidotetrelates in ionic liquids yields a 3D-framework (1), 0D-cluster anions (3) or a 2D-layered structure (2).

Acknowledgements: This work was supported by the Deutsche Forschungsgemeinschaft within the frameworks of SPP 1415 and SPP 1708. References: [1] (a) J. Heine, S. Dehnen, Z. Anorg. Allg. Chem. 2012, 638, 2425; (b) T. Wu, X. Wang, X. Bu, X. Zhao, P. Feng, Angew. Chem. 2009, 121, 7340. [2] Y. Lin, S. Dehnen, Inorg. Chem. 2011, 50, 7913. [3] G. Xu, C. Wang, P. Guo, Acta Crystallogr. 2009, C65, m171. [4] S. Santner, S. Dehnen, Inorg. Chem. 2015, 54, 1188-1190. [5] Y. Lin, W. Massa, S. Dehnen, J. Am. Chem. Soc. 2012, 134, 4497.

Poster presentation - P123

Probing Donor-Acceptor Interactions in peri-Substituted Diphenylphosphinoacenaphthyl-Element Dichlorides of Group 13 & 15 Elements Emanuel Hupf, Enno Lork, Stefan Mebs, Lilianna Chęcińska, Jens Beckmann [email protected] Institut für Anorganische Chemie, Universität Bremen Leobener Str, GER-28359, Bremen The reaction of ArLi with ECl3 (E = Al, P, In, Bi) and ArSnBu3 with ECl3 (E = B, Ga, Tl, Sb, Bi) proceeds via transmetallation reaction to give the diphenyl-phosphino-acenaphthyl-element dichlorides ArECl2 (Ar = 6-Ph2P-Ace-5-). The structural elucidation by single-crystal X-ray diffraction and DFT calculations showed that compounds of the series ArECl2adopt three different structure types (see Figure 1). All compounds of group 13 elements show a distorted tetrahedral arrangement at the triele atom and short P-E peri-distances, indicating attractive interactions between P and E (structure type A). Within the series of group 15 compounds two distinct structure types are observed depending on the environment. For ArECl2containing the elements P, As and Bi a T-shaped spatial arrangement with a nearly linear Cl-E-Cl linkage and short P-E peri distances are observed (type B). In contrast, ArSbCl2 shows a nearly rectangular Cl-E-Cl linkage with a long P-Sb peridistance, which is associated with repulsive interactions (type C).[1]

Figure 1. Different structure types within the series of compounds ArECl2.

References: [1] E. Hupf, E. ork, S. Mebs, . Chęcińska, J. Beckmann, Organometallics, 2014, 33, 7247.

Poster presentation - P124

Straightforward formation of the unprecedented 5-membered annulated ring containing the B-N moiety: 1H-2,1-benzazaborolyl alkali metal salts, reactivity with electrophiles and redox behavior Martin Hejda, Roman Jambor, Aleš Růžička, Antonín yčka and ibor Dostál [email protected] Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice Studentská 573, CZ - 532 10, Pardubice, Czech Republic 1,2-azaborolyl anion is known in the literature for a long time and already has been used as ligand for both transition and main group metals as cyclopentadienyl class ligand analogues.[i,ii] However, there are no reports dealing with analogous benzannulated 1H-2,1-benzazaboroles (Fig. 1C) in this respect. Recently, we have found,[iii] that reduction of variously substituted C,N-chelated chloroboranes (Fig. 1A) with potassium metal afforded various derivatives of symmetric (3,3’)-bis(1H-2,1benzazaborole) (Fig. 1B). Subsequent reduction of these compounds with two equivalents of alkali metal (M = Li, Na or K) proceeds via unique reaction pathway and produced the first 1H-2,1-benzazaborolyl (Bab) alkali metal salts M+(THF)(Bab)(Fig. 1C). These salts are extremely strong reducing agents. Nevertherless, they are still able to react with simple electrophiles under formation of substituted 1H-2,1benzazaboroles, but they also convert with starting C,N-chelated chloroboranes to unsymmetrically substituted (3,3’)-bis(1H-2,1-benzazaborole), thereby opening a new strategy for preparation of such C-C bridged heterocyclic systems. Reaction mechanisms, molecular structures, some experimental data and the latest results will be reported.

Figure 1.

Acknowledgements: The authors wish to thank the Grant Agency of the Czech Republic project No. P207/12/0223. References: [i] (a) G. Schmid, Comments Inorg. Chem., 1985, 4, 17-32. (b) S.-Y. Liu, M.-C. Lo, G. C. Fu, Angew. Chem. Int. Ed., 2002, 41, 174-176. [ii] For example see: A. J. Ashe III, Organometallics, 2009, 28, 4236-4248. [iii] M. Hejda, R. Jambor, A. Růžička, A. yčka, . Dostál, Dalton Trans. 2014, 43, 9012-9015.

Poster presentation - P125

Catalytic Dehydrogenation of Amino Boranes – Formation of Condensed Borazine Compounds Fabian Müller, Monica Trincado, and Hansjörg Grützmacher* [email protected] Laboratory of Inorganic Chemistry, Department of Chemistry and Applied Biosciences, ETH Zurich Vladimir-Prelog-Weg 1, 8093 Zurich, Switzerland Amino boranes are studied as fuels with respect to hydrogen storage and as precursors for inorganic materials. Thermal decomposition leads to polymeric BN compounds in form of nanotubes, nanoparticles or clusters.[1] With a new Ru diazadiene diolefin complex we achieved the synthesis of condensed borazine compounds (Figure 1). Remarkably, these poly(borazines) are soluble and contain likely polycondensed rings up to B50N49H28 and only little insoluble polymeric material is formed.[2]

Figure 1. Reaction equation of dehydrogenation of amino boranes.

References: [1] U. Kusari, Z. Bao, Y. Cai, G. Ahmad, K. H. Sandhage, L. G. Sneddon, Chem. Commun. 2007, 1177–1179. [2] M. Trincado, H. Grützmacher, Unpublished Results, 2015.

Poster presentation - P126

Titanocene-based Catalysts for Amine Borane Dehydrocoupling: Studies of the Mechanistic Role of Ti(III) Species and Formation of Polyaminoboranes Titel Jurca, Ian Manners* [email protected] School of Chemistry, University of Bristol Cantock’s Close, BS8 1TS, Bristol, UK Catalytic dehydrocoupling/dehydrogenation of amine-boranes has become a field of intense interest and rapid growth; largely driven by potential applications in hydrogen storage, transfer hydrogenations, and synthesis of novel inorganic polymers. Consequently, a wide variety of catalyst systems have been developed to promote this reaction, with the majority based on rare and expensive late transition metals.[1] Our group has previously reported that Group 4 metallocene [Cp2Ti] is an efficient homogeneous catalyst for the dehydrogenation of secondary amine-borane adducts R2NH·BH3 (R = Me, iPr). Prior mechanistic understanding of this reaction centered around the interplay of Ti intermediates in the +2 and +4 oxidation states.[2] Our group had previously reported the isolation of paramagnetic Ti III species as potential intermediates in the catalytic dehydrogenation process.[3] We report the synthesis of several new TiIII species, and their catalytic activity for the dehydrocoupling of secondary amine-boranes. Our results reinforce that paramagnetic TiIII species play a role in the dehydrogenation chemistry. Moreover, we have recently found that modifications to the ligand framework can have drastic effects on catalyst performance. For example, several new variants of our titanocene-based catalysts display not only a ten-fold increase in activity for the dehydrocoupling of secondary amine-boranes, but are also active as dehydropolymerization catalysts for primary amine-boranes; the first example of early transition metal amine-borane polymerization catalysts.

Acknowledgements: Naomi Stubbs, Dr. George R. Whittell, Dr. Erin M. Leitao. References: [1] E. M. Leitao, T. Jurca, I. Manners, I. Nature Chem. 2013, 5, 817-829. [2] (a) T. J. Clark, C. A. Russell, I. Manners, J. Am. Chem. Soc. 2006, 128, 9582-9583. (b) M. E. Sloan, A. Staubitz, T. J. Clark, C. A. Russell, G. C. Lloyd-Jones, I. Manners, I. J. Am. Chem. Soc. 2010, 132, 3831-3841. [3] H. Helten, B. Dutta, J. R. Vance, M. E. Sloan, M. F. Haddow, S. Sproules, D. Collison, G. R. Whittell, G. C. Lloyd-Jones, I. Manners, Angew. Chem. Int. Ed. 2013, 52, 437-440.

Poster presentation - P127

1,2-Azaborine, the BN derivative of ortho-benzyne Klara Edel,(a) Sarah A. Brough,(a) Ashley N. Lamm,(b) Shih-Yuan Liu,b,c Holger F. Bettingera,* [email protected] Institut für Organische Chemie, Universität Tübingen (a)Auf der Morgenstelle 18, 72076 Tübingen, Germany, (b) Department of Chemistry and Biochemistry, University of Oregon, Eugene, Oregon 97403-1253, United States, (c) Department of Chemistry, Boston College, Chestnut Hill Ortho-benzyne 1 is a well-known and extremely useful reactive intermediate in organic chemistry. The formal substitution of the CC-triple bond by an isoelectronic BN bond relates 1 to the azaborine 2. Here we show by direct spectroscopic techniques that 1,2-azaborine can exist as reactive intermediate. We found that 2 can be generated by flash vacuum pyrolysis (FVP) from precursor 3 by thermal elimination of t-butyldimethylsilylchloride (TBSCl) and isolated in cryogenic matrices. 1,2-Azaborine spontaneously binds dinitrogen N2 (adduct 4) in a photochemically reversible transformation.

Figure 1. Generation of 1,2-azaborine (2) by FVP of 3 and trapping with N2.

Acknowledgements: The research was supported by the Deutsche Forschungsgemeinschaft and the National Institutes of Health (Grant R01-GM094541). References: [1] For selected reviews on aryne chemistry, see: (a) C. M. Gampe and E. M. Carreira, Angew. Chem., Int. Ed. Engl., 2012, 51, 3766-3778; (b) P. M. Tadross and B. M. Stoltz, Chem. Rev., 2012, 112, 35503577; (c) H. Yoshida and K. Takaki, Synlett, 2012, 23, 1725-1732; (d) A. Bhunia, S. R. Yetra and A. T. Biju, Chem. Soc. Rev., 2012, 41, 3140-3152; (e) C. Wentrup, Aust. J. Chem., 2010, 63, 979-986; (f) T. Kitamura, Aust. J. Chem., 2010, 63, 987-1001; (g) H. H. Wenk, M. Winkler and W. Sander, Angew. Chem., Int. Ed. Engl., 2003, 42, 502-528; (g) H. Pellissier and M. Santelli, Tetrahedron, 2003, 59, 701730.

Poster presentation - P128

Fragmentation vs. Dehydogenation of Borazines Peter Grüninger, Holger F. Bettinger* [email protected] Institut für Organische Chemie, Universität Tübingen Auf der Morgenstelle 18, 72076 Tübingen, Germany A well-known concept to manipulate the electronic properties of polycyclic aromatic hydrocarbons, nanographenes, and possibly graphene is the isoelectronic substitution of CC by BN units.[1] Our interest is the flash vacuum pyrolysis (FVP) and photochemistry of borazine containing aromatic compounds, such as 1-3. We investigate competition of the dehydrogenation (path I) and fragmentation (path II) into reactive molecules using matrix isolation techniques.

Figure 1. Borazine containing aromatic compounds 1-3 and possible reactions, dehydrogenation (path I) to BN-HBC (5) and cycloreversion (path II) to dibenz[c,e][1,2]azaborine (4), exemplified for 3.

Acknowledgements: This research was supported by the Deutsche Forschungsgemeinschaft. References: [1] (a) M. J. D. Bosdet, W. E. Piers, Can. J. Chem., 2009, 87, 8; (b) P. G. Campbell, A. J. V. Marwitz, S.-Y. Liu, Angew. Chem. Int. Ed., 2012, 51, 6074; (c) S.-M. Jung, E. K. Lee, M. Choi, D. Shin, I.-Y. Jeon, J.-M. Seo, H. Y. Jeong, N. Park, J. H. Oh, J.-B. Baek, Angew. Chem. Int. Ed.,2014, 53, 2398; (d) X.-Y. Wang, F.-D. Zhuang, X.-C. Wang, X.-Y. Cao, J.-Y. Wang, J. Pei, Chem. Commun.,2015, 51, 4368; (e) X.-Y. Wang, J.-Y. Wang, J. Pei, Chem. Eur. J.,2015, 21, 3528; (f) M. Müller, S. Behnle, C. Maichle-Mössmer, H. F. Bettinger, Chem. Commun., 2014, 50, 7821.

Poster presentation - P129

Cationic and Anionic Chains of only Lewis Base Stabilised Pnictogenylboranes Christian Marquardt, Manfred Scheer* [email protected] Institute of Inorganic Chemistry, University of Regensburg Universitätsstraße 31, GER-93053, Regensburg In the recent years the interest in the chemistry of compounds containing Group 13/15 elements increased considerably. Especially the borane adducts of nitrogen-donors containing a high percentage of hydrogen are intensively discussed as new hydrogenstorage materials.[1] Surprisingly, borane adducts of phosphorus-donors or even heavier analogs have not been studied thoroughly yet. Recently, we reported about a new and convenient way to synthesize the parent and mixed substituted pnictogenylboranes, which were not accessible by previously published methods.[2] The pnictogenylboranes “H2EBH2·NMe3” (E = P, As) serve as readily available building blocks for mixed Group 13/15 element cationic chains.[3] In addition, first examples of anionic species have also been obtained. These unprecedented molecules show a rich subsequent chemistry, including the formation of extended chain molecules. Furthermore they can be used for the synthesis of inorganic polymers, or as precursors for 13/15 composite materials.

Figure 1. Selected pnictogenylborane chains.

Acknowledgements: DFG and COST action CM1302 are gratefully acknowledged. References: [1] A. Staubitz, A. P. M. Robertson, I. Manners, Chem. Rev. 2010, 110, 4023. [2] C. Marquardt, A. Adolf, A. Stauber, M. Bodensteiner, A.V. Virovets, A. Y. Timoshkin, M. Scheer, Chem. Eur. J. 2013, 19, 11887. [3] C. Marquardt, C. Thoms, A. Stauber, G. Balázs, M. Bodensteiner, M. Scheer, Angew. Chem. Int. Ed. 2014, 53, 3727.

Poster presentation - P130

Cooperative Al/P Lewis Pairs Based on Cationic Aluminium Complexes Tom Stennett, Jürgen Pahl, Sjoerd Harder* [email protected] Institut für Anorganische Chemie, Friedrich-Alexander-Universität Erlangen Nürnberg Egerlandstraße 1 91058 Erlangen Germany The unquenched interaction of Lewis acids and bases that cannot form adducts due to steric repulsion was introduced in 2006 as a concept for stoichiometric and catalytic transformations of small molecules.[1] Recently, this approach has been extended to acid/base pairs that, despite reduced steric encumbrance, do not interact strongly due to poor orbital overlap and/or mismatched polarizability.[2] Cationic, coordinatively unsaturated aluminium complexes, [NacnacAlMe][B(C6F5)4] (Nacnac = βdiketiminate) undergo intramolecular reactions with alkenes,[3] alkynes, CO2 and epoxides. However, these reactions tend to have unstable products and involve ligand non-innocence. Addition of a phosphine to such cationic complexes results in varying degrees of Al-P interaction, depending on the phosphine employed. Systems based on PPh3, PtBu3 and a phosphine-substituted β-diketiminate provide a wide range of frustrated Lewis pair type reactivity at the metal centre, including the binding of unsaturated small molecules and the catalytic dehydrocoupling of Me2NH-BH3.

Figure 1. Small molecule activation with a cooperative Al+/P pair.

References: [1] G. C. Welch, R. R. San Juan, J. D. Masuda, D. W. Stephan, Science 2006, 314, 1124–1126. [2] S. Roters, C. Appelt, H. Westenberg, A. Hepp, J. C. Slootweg, K. Lammertsma, W. Uhl, Dalton Trans. 2012, 41, 9033. [3] C. E. Radzewich, M. P. Coles, R. F. Jordan, J. Am. Chem. Soc. 1998, 120, 9384.

Poster presentation - P131

Binary Group 13/14 and 13/15 Zintl Anions and Their Reactions towards Ternary Intermetalloid Clusters Niels Lichtenberger, Stefanie Dehnen* [email protected] Department of Chemisty, Philipps University of Marburg Hans-Meerwein-Straße, GER-35043, Marburg Intermetalloid clusters that combine main group (semi-)metals with transition metals belong to the most recent developments in the field of Zintl anion chemistry, attracting both chemists and physicists due to their unique structural and electronic properties.[1] Recently, we were able to extend the field to the use of small binary anions comprising triel elements (TrBi3)2– (Tr = Ga, In), which have proven to be powerful synthetic building blocks for new polyanionic clusters.[2] Our results led us to investigate the chemistry of the binary Zintl anions with the heaviest triel metal thallium. Thereby, we were able to isolate a variety of new anions and gain more insight into the influence of the triel element on reaction products and relative stabilities. Furthermore, new and unprecedented intermetalloid clusters with intriguing electronic and structural properties were obtained. To enable a better understanding of the bonding situations and to allow for reliable atom assignments we employed quantum chemical methods

Figure 1. Intermetalloid cluster anions K2[Tl@Tl7Pb5]4– (left) and [Bi6-(µ3-Zn)3-Bi5Tl]4– (right).

References: [1] S. Scharfe, F. Kraus, S. Stegmaier, A. Schier, T. F. Fässler, Angew. Chem. Int. Ed. 2011, 50, 3630. [2] a) B. Weinert, F. Weigend, S. Dehnen, Chem. Eur. J. 2012, 18, 13589; b) B. Weinert, A.R. Eulenstein, R. Ababei, S. Dehnen, Angew. Chem. Int. Ed. 2014, 53, 4704; c) B. Weinert, F. Müller, K. Harms, R. Clérac, S. Dehnen, Angew. Chem. Int. Ed. 2014, 53, 11979-11983.

Poster presentation - P132

Toward Connection of Aromatics and Ruthenium Complexes to Tin/Sulfur Clusters Eliza Leusmann Stefanie Dehnen* [email protected] Department of Chemistry, Philipps-University Marburg Hans-Meerwein-Str. 4, 35043 Marburg, Germany In recent years, the design of ruthenium complexes has attracted great interest due to their properties which are useful for diverse applications like in dye-sensitized solar cells[1], as chromophores[2] or in water oxidation[3]. Many of these complexes include N-donor, chelating ligands like terpyridines.[1] In our group, we have developed the ligands of organotetrelchalcogenide cages, especially a double-decker-like RSn/S cluster based on an inorganic Sn4S6 core. Starting out from a ketofunctionalized ligand R = CMe2CH2COMe, reactions with hydrazine derivatives have been successful. To combine the versatile properties of the inorganic cluster core with the potentially applicable properties of Ru(II) complexes, one of our aims is to attach these to an Sn/S cage. This can be achieved either by functionalization of the Sn/S cluster with a suitable donor ligand and subsequent Ru(II)-semisequestration or by attachment of a pre-formed Ru(II) complex to the cluster - like connection of acetylruthenocene[5]. Newest research shows that attachment of chelating ligands to the Sn/S cluster is possible, e.g. bipyridine and chinoline.[6]

Figure 1. Molecular structure of the ruthenocenyl-decorated Sn/S cluster. Acknowledgements: We thank the DFG-GRK 1782 for financial support. References: [1] P. G. Bomben, T. J. Gordon, E. Schott, C. P. Berlinguette, Angew. Chem. 2011, 123, 10870-10873. [2] K. C. D. Robson, C. P. Berlinguette et al., Inorg. Chem. 2011, 50, 5494-5508. [3] B. Radaram, X. Zhao et al., Inorg. Chem. 2011, 50, 10564-10571. [4] Z. Hassanzadeh Fard, L. Xiong, C. Müller, M. Holynska, S. Dehnen, Chem. Eur. J. 2009, 15, 65956604. [5] E. Leusmann, M. Wagner, N. W. Rosemann, S. Chatterjee, S. Dehnen, Inorg. Chem. 2014, 53, 4228-4233. [6] E. Leusmann, F. Schneck, S. Dehnen, submitted.

Poster presentation - P133

Ag(I) Coordination Polymers of Cyclophosphazenes Derya Davarc , unus Zorlu, Rüştü Gür, Serap Beşli [email protected] Department of Chemistry Gebze Technical University, 41400, Kocaeli, Turkey. Hexachlorocyclotriphosphazene (trimer) and octachlorocyclotetraphosphazene (tetramer) which are inorganic heterocyclic rings have used in many studies because of having reactive P-Cl bounds. Cyclophosphazene compounds are capable to bind metal ions through endocyclic and exocyclic ring nitrogen atoms. Especially, trimer derivatives containing pyridyloxy groups have used as ligand in the literature [1-4]. In this study we have synthesized new silver (I) coordination polymers by using trimer and tetramer ligands. We have targeted to obtain metal organic framework of these coordination compounds and to focus on the effect of ring size and number of donor atoms on crystal structures.

Figure 1. Crystal structures of Ag(I) coordination polymers (a) trimer and (b) tetramer.

Acknowledgements: The authors would like to thank the Scientific and Technical Research Council of Turkey for financial support (grant 114Z566) References: [1] V. Chandrasekhar, R. S. Narayanan, Dalton Trans., 2013, 42, 6619-6632. [2] E. W. Ainscough, A. M. Brodie, R. J. Davidson, C. A. Otter, Inorg. Chem. Commun., 2008, 11, 171–174 . [3] E. W. Ainscough, A. M. Brodie, P.J.B. Edwards, G.B. Jameson, C. A. Otter, S. Kirk, Inorg. Chem., 2012, 51, 10884-10892. [4] E. W. Ainscough, A. M. Brodie, C. V. Depree, A. Derwahl, B. Moubaraki, K. S. Murry, C. A. Otter, Dalton Trans., 2005, 3337-3343.

Poster presentation - P134

Chiral Oxazoline Complexes of Basal Bulky Cobalt Sandwich Compounds and Cyclophosphazenes Jatinder Singh, Dheeraj Kumar and Anil J. Elias* [email protected] Department of chemistry, IIT Delhi Hauz Khas, New Delhi-110016 Among metal sandwich compounds, one of the best competitors for ferrocene with regard to stability, ease of synthesis and reaction chemistry is the 18 electron cobalt sandwich compound [(η5-Cp)Co(η4-C4Ph4)]. While the molecule as such is much less reactive than ferrocene, its cyclopentadienyl derivatives, especially the carboxylate ester has shown excellent potential for developing novel chiral organometallic catalysts for asymmetric synthesis ably assisted by the bulky tetraphenylcyclobutadiene moiety. Monomeric and dimeric palladacycles based on (η5-Cp)Co(η4-C4Ph4) and [(η5-Cp)Co(η4-C4Ph3)]2 are well documented with established utility in homogeneous asymmetric catalysis. However, all these cobalt sandwich based palladacycles have the chiral binding moiety positioned on the cyclopentadienyl ring and the palladacycles were formed from a C-H activation followed by cyclopalladation of the cyclopentadienyl bound protons. Six membered cyclophosphazene ring can also act as an excellent precursor for preparing multioxazoline ligands having C2 and C3 axis, which can play a critical role in determining the enantioselectivity of a catalytic reaction In this presentation, we report the synthesis and structural characterization of the first examples of a new type of [(η5-RCp)Co(η4-C4Ph3R')] type bisoxazoline having chiral oxazolinyl units on both the cyclobutadiene and cyclopentadienyl rings of the cobalt sandwich compound and the first examples of C2 and C3- symmetric chiral oxazoline derivatives of cyclophosphazenes. Preliminary studies on such compounds indicated that these ligands have the potential to form a range of transition metal based chiral catalysts.

References: Singh, J.; Kumar, D.; Singh, N.; Elias, A. J., Organometallics, 2014, 33, 1044-1052. Kumar, D.; Singh, J.; Elias, A. J. Dalton Trans. 2014, 40, 4882-4891.

Poster presentation - P135

Luminescent complexes of copper(I) halides with functionalized tertiary phosphines Peter Bartos, Petr Taborsky, Marek Necas [email protected] Department of Chemistry, Faculty of Science, Masaryk University Kotlarska 2, CZ-61137, Brno, Czech Republic Depending on copper(I) halide, ligand to metal ratio and reaction conditions, complexes with various central CuX clusters can be prepared. Compounds containing central Cu4(μ3-I)4cubane-like clusters in their structures have been intensively studied because of their thermochromic behavior.[1] A series of reactions of copper(I) halides with P(III)-containing ligands was carried out in different molar ratios in different solvents, yielding new Cu(I) complexes, which were characterized by 31P NMR and X-ray diffraction. The P(III)-containing ligands were based on tertiary phosphines carrying at least one organic functional group (e.g. CN, COOH) on the alkyl/aryl substituents. Luminescence in the complexes and its dependence on various conditions (solvent, temperature) was also studied.

Acknowledgements: To Mr. Michal Babiak and CEITEC´s X-ray Diffraction and Bio-SAXS Core Facility for X-ray measurements. European Regional Development Fund (CZ.1.05/1.1.00/02.0068). References: [1] (a) X.-C. Shan, F.-L. Jiang, H.-b. Zhang, X.-Y. Qian, L. Chen, M.-Y. Wu, S. A. AL-Thabaiti, M.-C. Hong, Chem. Commun., 2013, 49, 10227; (b) X.-C. Shan, F.-L. Jiang, L. Chen, M.-Y. Wu, J. Pan, X.Y. Wan, M.-C. Hong, J. Mater. Chem. C, 2013, 1, 4339.

Poster presentation - P136

Self-Assembly of a Luminescent Thiolato-Stabilized Hexanonacontanuclear Cuprous Wheel C. W. Liu,* Jhih-Yu Cyue, Bing Li, Jian-Hong Liao [email protected] Department of Chemistry, National Dong Hwa University No 1, Sec. 2, Da Hseuh Rd. Hualien, Taiwan 97401 A cuprous wheel containing hexanonacontanuclear thiolate-bridged copper(I) cluster, [Cu96{SC(O)OiPr}96] 1, was obtained through self-assembly of copper salts with asymmetrical O-isopropyl monothiocarbonate ligand in acetone. X-ray crystalstructure analysis reveals that 1 crystallizes in the trigonal space group R(-)3 with a protein-sized six-gear-like macrocyclic structure, which comprises 96 copper(I) ions bridged by 96 O-isopropyl monothiocarbonate ligands. The molecule possesses a S6 axis, therefore only sixteen unique Cu(I) ions and sixteen ligands present in the asymmetric unit and all atoms are located in general positions. The compound 1 exhibits an orange-yellow emission in the solid state at ambient temperature and at 77K upon irradiation with an UV lamp. Upon dissolving in solvents such as ethanol, methanol, acetonitrile, and dihalomethane at 298 K, the emissive phenomena differ. The dihalomethane solution produces a red luminescence, which is red shift of the maximum emission by ca. 3400 cm−1 compared to luminescence of the crystalline solid, but no emission is detected in ethanol, methanol and acetonitrile. However, upon freezing in a liquid N2bath, all these glasses exhibit brilliant yellow luminescent, which are blue-shift (by ca. 277−30 cm−1), and intensity increase relative to solidstate luminescence at 77 K. The luminescence feature displayed by dihalomethane suggests that compound 1 is a potential sensor for halogenated species.

Acknowledgements: Financial Supports from Ministry of Science and Technology in Taiwan

Poster presentation - P137

Hexanuclear and Tetranuclear Titanium Organophosphonates Formed via a Common Single-4-Ring Intermediate: Insights into Formation Pathways Kamna Sharma, Alok Ch. Kalita, Paul Davis and Ramaswamy Murugavel* [email protected] Deparment of Chemistry Indian Institute of Technology, Bombay Powai-400076, Mumbai, Maharashtra India Reactivity of diketonate modified titanium precursor [Ti(acac)2(OiPr)2] with tert-butyl phosphonic acid at two different ratios of the reactants has been investigated. Reaction of an equimolar quantities of tBuP(O)(OH)2and [Ti(acac)2(OiPr)2] in CH2Cl2 followed by crystallization in CH2Cl2yields the hexanuclear titanophosphonate cluster [Ti6(µ-O)2(µ-tBuPO3)6(acac)6(OiPr)2] (1), presumably formed through the hydrolysis of a symmetric intermediate [Ti6(µ-tBuPO3)6(acac)6(OiPr)6] (A) that is similar to the D6R SBU of zeolites. Interestingly, when the same reaction has been carried out in acetonitrile, a related but an asymmetric hexanuclear cluster [Ti6(µ-O)3(µ-tBuPO3)5(µt BuPO3H)(acac)6(OiPr)] (2) has been isolated, which has also presumably formed from A via 1 through further hydrolysis. Reaction of 1.5 equivalents of the phosphonic acid with one equivalent of [Ti(acac)2(OiPr)2] in acetonitrile however leads to the fortmation of a symmetric tetranuclear titanophosphate cluster [Ti4(µOH)2(µ-tBuPO3)4(µ-tBuPO3H)2(acac)4] (3), which is essentially a fusion product of S4R titanium phosphonate [Ti(acac)(OiPr)(O3PtBu)]2 in the presence of excess phosphonic acid and small quantities of adventitious water. The titanium clusters 1-3 have been characterized by analytical and spectroscopic techniques apart from single crystal X-ray diffraction studies. The adjacent pair of titanium centers is bridged by µO2- ligands in 1 and 2 and a µ-OH‑ ligand in 3. All the three clusters are held together by multiply bridging phosphonate ligands displaying either in [3.111] or [3.110] binding mode. A common structural feature in all the three compounds is the presence of Ti2O4P2 ring, which is the basic building block (S4R) that is formed in the early stages of cluster development in these phosphonate clusters.

Acknowledgements: This work was supported by DST, New Delhi and DAE-BRNS, Mumbai. R.M. thanks BRNS for a DAE-SRC Outstanding Investigator Award. KS thanks CSIR, New Delhi for research scholrship.

Poster presentation - P138

Structural Characterization and Luminescence Studies of Au(I) Complexes with PNP and PNB Based Ligand Systems Shabana Khan [email protected] Department of Chemistry, Indian Institute of Science Education and Research (IISER) Pune Dr. Homi Bhaba Road, Pune-411008, India The PNP and PNB framework based gold(I) complexes have been synthesized and studied for their structural and luminescence properties. In case of PNP based system, reaction of corresponding L→AuCl with AgSbF6 yielded a fully supported dimeric dinuclear Au(I) cation 1 while PNB system led the formation of dimeric mononuclear Au(I) cation 2.[1] The molecular structure of 1 reveals the presence of a strong intramolecular aurophilic interaction with a Au····Au bond distance of 2.758(1) Å, one of the shortest aurophilic interactions reported in literature. However, cation 2 displays no aurophilic interaction. The effect of aurophilic interaction is also illustrated through the study of the luminescent properties of these gold(I) complexes. Cation 1 in which aurophilic interaction is present, exhibits blue luminescence in solution as well as in the solid state whereas the other gold(I) complexes remain nonluminescent.

Figure 1. (a) PNP and PNB based Au(I) Cations; (b) Normalized emission spectrum and picture of solution and solid state emission under UV light for PNP based Au(I) cation 1.

Acknowledgements: S.K. thanks SERB(India) and IISER Pune for financial support. References: [1] S. Pal, N. Kathewad, S. Khan (manuscript under preparation).

Poster presentation - P139

A Bimetallic Phosphorous-Based Complex as a Building Block to Form Organometallic-Organic Hybrid Materials Mehdi Elsayed Moussa, Bianca Attenberger, Stefan Welsch, Manfred Scheer* [email protected] University of Regensburg, Institute of Inorganic chemistry Universitatsstr. 31, GER-93053 Regensburg.

In the past thirty years research into porous materials resulted in a number of important technological applications.[1] In this field our group is interested in the use of organometallic complexes based on polyphosphorus ligands as bridging units between metal centers.[2] These complexes allow the formation of one- and twodimentional polymers[3] as well as giant spherical molecules.[4] In one approach the compound A was synthesized from the reaction between [Cp2Mo2(CO)4(η2-P2)] and the silver salt Ag[Al{OC(CF3)3}4].[5] The reactions of A with the pyridine-based ditopic ligands 1-4 have lead the formation of a large variety of assemblies B-F.[6] This novel synthetic route will open up new opportunities to incorporate defined functionalities in solid-state architectures of phosphorus ligand complexes.

Acknowledgements: The European Research Council (ERC-2013-AdG 339072) is gratefully acknowledged for the support of this work. References: [1] J-R. Li, J. Sculley, H.-C. Zhou, Chem. Rev. 2012, 112, 869 (and references herein). [2] M. Scheer, Dalton Trans, 2008, 33, 4372. [3] J. Bai, J. V. Virovets, M. Scheer, Angew. Chem. Int. Ed. 2002, 41, 1737. [4] J. Bai, J. V. Virovets, M. Scheer, Science, 2003, 300, 781. [5] M. Scheer, L.J. Gregoriades, M. Zabel, et al., Chem. Eur. J. 2008, 14, 282. [6] B. Attenberger, S. Welsch, M. Zabel, E. Peresypkina, M. Scheer, Angew. Chem. Int. Ed. 2011, 50, 11516.

Poster presentation - P140

Synthesis, crystal structure and properties of ferrocenyl based pyridyl functionalized dithiocarbamate complexes of group 12 metals Vinod Kumara, Michael G. B. Drewb and Nanhai Singh* [email protected] Department of Chemistry, Banaras Hindu University Varanasi-221005 A developing interest in the dithiocarbamate ligand chemistry is due to their functionalization which may potentially give rise to intriguing structures and tunable physical properties. Transition metal dithiocarbamate complexes have been extensively studied due to their important material properties and myriad of applications.[1-2] In this presentation new ferrocenyl based robust macrocyclic ring metal-organic coordination polymers and dinuclear complexes involving 3- and 4pyridyl functionalized dithiocarbamate complexes of the form [M(dtc)2] (dtc = ferrocenyl pyridin-3-ylmethyldithiocarbamate, M = Zn(II) 1, Cd(II) 2, Hg(II) 3); dtc = ferrocenyl pyridin-4-ylmethyldithiocarbamate, M = Zn(II) 4, Cd(II) 5, Hg(II) 6)), have been synthesized and fully characterized and their structures have been elucidated by X-ray crystallography. Their luminescent properties and uses as single source precursor for the preparation of mixed-metal sulphide materials are being investigated.

Figure 1. A Zn(II) dimer and a Cd(II) polymer synthesized from the dithiocarbamate (dtc) ligand.

Acknowledgements: Financial support from the Science and Engineering Reserach Board (SERB,SB/S1/IC-15/2014) New Delhi, is gratefully acknowledged. References: [1] G. Hogarth, Prog. Inorg. Chem., 2005, 53, 71– 561. [2] A. Kumar, R. Chauhan, K. C. Molloy, G. K. Köhn, L. Bahadur and N. Singh, Chem. – Eur. J., 2010, 16, 4307–4314. (b) V. Singh, R. Chauhan, A. N. Gupta, V. Kumar, M. G. B. Drew, L. Bahadur and N. Singh, Dalton Trans., 2014, 43, 4752–4761.(c) V. Kumar, V. Singh, A. N. Gupta, M. G. B. Drew and N. Singh, Dalton Trans., 2015, 44, 1716–1723.

Poster presentation - P141

Ligand Protected Zinc Clusters Hung Banh, Kerstin Freitag, Katharina Dilchert, Christine Schulz, Christian Gemel, Rüdiger W. Seidel, Samia Kahlal, Jean-Yves Saillard, Roland A. Fischer* [email protected] Chair of Inorganic Chemistry II, Ruhr-University Bochum Universitätsstr. 150, GER-44801, Bochum Ligand protected metal clusters [Ma]Lb linking molecular and bulk materials have been in the focus of research for a very long time. In particular, metalloid Al and Ga clusters (a>b) have attracted substantial interest.[1] Recently it has been predicted by calculations that related metalloid zinc clusters have a large spectrum of electronic properties ranging from a metallic to an insulating character, depending on the cluster size, also exhibiting unique features, which combine both phenomena.[2] Naked zinc clusters have been experimentally studied in the gas phase,[2] or hosted in Zeolite X[3] or intermetallic frameworks, respectively.[4] However, ligand protected (metalloid) clusters [Zna]Lb remained unknown, so far. Herein, we present the preparation, structural characterization and bonding analysis of first ligand protected zinc clusters {[Zn3]Cp*3}+ (1),[5] [Zn9]Cp*6 (2) and {[Zn10](Cp*6Me)}+ (3). The synthetic access of these clusters is based on the reaction of [Zn2Cp*2] with [ZnCp*2] or ZnMe2 in the presence of [H(Et2O)2][BAr4F] or [(C5H5)2Fe][BAr4F]+, the latter acting as a selective reagent for the removal of the protecting group Cp* (= C5Me5). The reaction mechanism involving alkyl-group transfer and disproportionation of intermediate Zn(I) species as well as the electronic structure of these clusters will be discussed.

Figure 1. Series of first examples of ligand protected zinc clusters.

References: [1] H.-G. Schnöckel, Dalton. Trans. 2008, 4344-4362. [2] A. Aguado, A. Vega, A. Lebon, B. von Issendorff, Angew. Chem. Int. Ed., 2015, 54, 2111-2115. [3] S. Zhen, K. Seff, J. Phys. Chem. B, 1999, 103, 6493-6497. [4] (a) U. Häußermann, P. Viklund, C. Svensson, S. Eriksson, P. Berastegui, S. Lidin, Angew. Chem. Int. Ed., 1999, 38, 488-492; (b) P. Viklund, C. Svensson, S. Hull, S. I. Simak, P. Berastegui, U. Häußermann, Chem. Eur. J., 2001, 7, 5143-5152. [5] K. Freitag, C. Gemel, P. Jerabek, M. I. Oppel, R. W. Seidel, G. Frenking, H. Banh, K. Dilchert, R. A. Fischer, Angew. Chem. Int Ed., 2015, DOI: 10.1002/anie.201410737.

Poster presentation - P142

Zinc-Zinc Interactions in Zinc Containing Complexes and Clusters Kerstin Freitag, Christian Gemel, Rüdiger Seidel, Paul Jerabek, Gernot Frenking and Roland A. Fischer* [email protected] Inorganic Chemistry II, Ruhr-University Bochum Universitätsstraße 150, GER-44801, Bochum On the molecular scale, interactions of organozinc units with transition metals have become important and many compounds and clusters have been reported in the recent past.[1] In this context of our studies, the triangular compounds [Zn3Cp*3]+ and [Zn2CuCp*] can be described as the most simple „building blocks“ for zinc and mixed metal clusters. Theoretical calculations demonstrate a σ-aromatic nature and thus strong analogies to the electronic structure of [H3]+.[2] Following there is an analogy between H2and the .ZnCp* dimer [Zn2Cp*2], also shown by simple „addition reactions“ of [Zn2Cp*2] to transition metal centers LnM, forming complexes of the general type [LnM(ZnCp*)2], which mirrors „oxidative addition“ reactions of H2 to electron rich unsaturated transition metal fragments. Against this background the investigation of Zn2M complexes exhibiting Zn-Zn interactions, as analogues to nonclassical dihydrogen Kubas type complexes, aroused our interest.[3] Very recently complexes, revealing shorter Zn-Zn distances as found for the (distorted) hexagonal closest packed structure of metallic zinc (2.664(1) Å), have been isolated and characterized, namely [Ni(ZnCp*)(ZnMe)(PMe3)3] (d(Zn-Zn) = 2.525(1) Å) and [Pd(ZnCp*)4(CNtBu)2] (2.595(2) and 2.609(2) Å). Latest results on zinc-zinc interactions in zinc containing complexes and clusters, based on theoretical calculations as well as structural properties, are presented in this contribution.

Figure 1. Zn-Zn distances in [Zn2Cp*2], [Zn3Cp*3]+ and [Pd(ZnCp*)4(CNtBu)2].

References: [1] K. Freitag, H. Banh, C. Gemel, R. W. Seidel, S. Kahlal, J.-Y. Saillard, R. A. Fischer, Chem. Comm. 2014, 50, 8681-8684. [2] K. Freitag, C. Gemel, P. Jerabek, M. I. Oppel, R. W. Seidel, G. Frenking, H. Banh, K. Dilchert, R. A. Fischer, Angew. Chem. Int. Ed. 2015, 10.1002/anie.201410737R1. [3] G. J. Kubas, Proc. Natl. Acad. Sci. U. S. A. 2007, 104, 6901-6907.

Poster presentation - P143

Two Alternative Approaches to Access Mixed Hydride-Amido Zinc Complexes: Synthetic, Structural and Solution Implications Andrew J. Roberts, Stuart D. Robertson, Eva Hevia* [email protected] WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde Glasgow, G1 1XL, UK Molecular zinc hydrides have recently received much attention as non-precious metal catalysts for homogenous hydrosilylation and hydroboration processes.[1] However, despite this increasing interest, only a few well-defined examples are known.[1,2] Highlighting the structural and stoichiometric diversity in zinc-hydride chemistry, this poster explores the synthesis of NHC-stabilized mixed amido-hydride zinc complexes using bis(amide) Zn(HMDS)2 (HMDS= 1,1,1,3,3,3-hexamethyldisilazide) as a precursor and two alternative hydride sources, namely dimethylamine borane (DMAB) and phenylsilane PhSiH3 (Figure). By combining X-ray crystallography with advanced NMR spectroscopic studies (including DOSY NMR experiments), new insights into the constitution of these new compounds will be discussed.[3]

References: [1] (a) A. Rit, T.P. Spaniol, L. Maron, J. Okuda, Angew. Chem. Int. Ed., 2013, 52, 4664 (b) P.A. Lummis, M.R. Momeni, M.W. Lui, R. McDonald, M.J. Ferguson, M. Miskolzie, A. Brown, E. Rivard, Angew. Chem. Int. Ed., 2014, 53, 9351. [2] (a) J. Spielmann, D. Piesik, B. Wittkamp, G. Jansen, S. Harder, Chem. Commun. 2009, 3455. (b) A. Rit, T. P. Spaniol, L. Maron, J. Okuda, Organometallics, 2014, 33, 2039. [3] A. J. Roberts,W. Clegg, A. R. Kennedy,M. R. Probert,S. D. Robertson, E. Hevia, Dalton Trans. 2015, advance article.

Poster presentation - P144

Investigations on selenidozincates and –cadmates in ionic liquids Isabell Nußbruch, Stefanie Dehnen* [email protected] Department of Chemistry, Philipps University of Marburg Hans-Meerwein-Str. 4, D-35032 Marburg Recently the first top-down strategy for the deconstruction of a three-dimensional framework in ionic liquids was reported.[1] The starting material was the 3Dselenidostannate-framework 3D-K2[Sn2Se5] (3D-1), which was thermally converted in [BMIm][BF4] and the presence of an amine through a 2D layered phase (2D-1) to a 1D-chain structure (1D-1), back to a 3D-network (3D-2).[1] Furthermore, it is known that selenidomercurates as well as selenidocadmates form 2D-layered phases and 3Dframework structures.[2][3] Preparations of phases of KxZnySez and KxCdySez with different compositions followed by investigations on their behavior in and with ionic liquids are studied. The solid phases are obtained as powders by heating K2Se and ZnSe or CdSe in stoichiometric amounts in a quartz tube with an oxygen burner. Ionothermal treatment of these solid phases is expected to lead to new interesting structural changes and properties.

Figure 1. Illustration of the structural changes of 3D-K2[Sn2Se5] by ionothermal treatment.

References: [1] Y. Lin, D. Xie, W. Massa, L. Mayrhofer, S. Lippert, B. Ewers, A. Chernikov, M. Koch, S. Dehnen, Chem. - Eur. J. 2013, 19, 8806–8813. [2] M. G. Kanatzidis, Y. Park, Chem. Mater. 1990, 2, 99–101. [3] E. A. Axtell, J.-H. Liao, Z. Pikramenou, M. G. Kanatzidis, Chem. - Eur. J. 1996, 2, 656–666.

Poster presentation - P145

Bottom-Up! Intermetallic Nickel Gallium Molecular Clusters and Complexes as Potential Precursors for Intermetallic Nanoparticles Katharina Dilchert, Jana Weßing, Christian Gemel and Roland A. Fischer* [email protected] Chair of Inorganic Chemistry II – Organometallics & Materials Ruhr-University Bochum, Universitätsstr. 150, GER-44801, Bochum The low coordinate organo group 13 species ER (E = Al, Ga, In, R = Cp*, C(SiMe3)3, Cp* = pentamethylcyclopentadienyl) of oxidation state +I are potent ligands at transition metal centers and provide new perspectives for bottom-up intermetallic cluster and nano material synthesis. In particular, ECp* ligands (E = Ga, Al, In) are isolobal to CO, phosphines, NHC ligands and feature Cp* as fluxional and even removable group. For the d10 metal triad Ni, Pd and Pt a number of small clusters [Ma(ECp*)b] (a = 1, 2, 3)[1] is known. Such compounds show perspectives as precursors for bimetallic Ni/Ga nanoparticles (suitable catalysts for alkyne semihydrogenation) by hydrogenolysis or microwave induced decomposition in organic solvents or ionic liquids (ILs).[2] Interestingly, examples for high nuclearity clusters [MaLb] (a >> b, a >> 3) with L = PPh3 and/or CO are numerous. In contrast, for L = ECp* the maximum nuclearity of the d10 metal core remained at a = 3, so far. In this contribution we want to present the synthesis and characterization of [Ni8(GaCp*)6], the first example of a homoleptic “intermetalloid” cluster [Ma(ECp*)b] with a > b and a > 3. Single crystal XRD studies suggest a distorted cubic structure of the Ni8core, which is face-capped by six GaCp* ligands. Liquid injection field desorption mass spectrometry (LIFDI)-MS, however, reveals a dominant signal for [Ni7(GaCp*)6]+ and only traces of [Ni8(GaCp*)6]. The details on the synthesis, structural and spectroscopic characterization of [Nin(GaCp*)6] (n = 7, 8) as well as the decomposition of the cluster to yield bimetallic Ni/Ga nanoparticles will be presented and discussed.

Figure 1. Synthesis and structure of [Nin(GaCp*)6] (n =7,8) and LIFDI-MS data.

References: [1] T. Steinke, C. Gemel, M. Winter, R. A. Fischer, Chemistry – A European Journal 2005, 11, 16361646. [2] K. Schuette, A. Doddi, C. Kroll, H. Meyer, C. Wiktor, C. Gemel, G. van Tendeloo, R. A. Fischer, C. Janiak, Nanoscale 2014, 6, 5532-5544.

Poster presentation - P146

Incorporation of Small Molecules in Fullerene-like Supramolecules Claudia Heindl, Manfred Scheer* [email protected] Institute of Inorganic Chemistry, University of Regensburg Universitätsstraße 31, GER-93040 Regensburg Supramolecular aggregates with defined inner cavities are in focus of current research, especially because of their application as molecular container. A wide variety of metal complexes with vacant coordination sites and linking units act as building blocks for its preparation using the self-assembly concept. However, the linkage is mostly restricted to ligands with nitrogen or oxygen as donating atoms. It is shown, that also the use of pentaphosphaferrocene [Cp Fe(η5-P5)] (Cp* = C5Me5) and CuX (X = Cl, Br, I) enables the formation of discrete supramolecules. Their scaffold only consists of five- and six-membered rings and displays a non-carbon IhC80 fullerene analogue. In addition, they are capable to encapsulate small molecules, such as o-carborane[1] or ferrocene.[2] In order to examine the required properties of templates to be incorporated, different molecules with distinctive features were tested. Herein, we are able to present that also less symmetrical templates, like [(η7-C7H7)V(η5-C5H5)] and P4S3 can be trapped within the cavity of these spheres.

Figure 1. Scaffold of a 80-vertex nanoball (left) and the whole sphere with encapsulated P4S3 (right).

References: [1] M. Scheer, A. Schindler, C. Gröger, A. V. Virovets, E. V. Peresypkina, Angew. Chem. Int. Ed. 2009, 48, 5046. [2] A. Schindler, C. Heindl, G. Balázs, C. Groeger, A. V. Virovets, E. V. Peresypkina, M. Scheer, Chem. Eur. J. 2012, 18, 829.

Poster presentation - P147

Rational molecular design: common-sense chemistry R. Andrew Davies,* Michael A. Beckett, Charlotte L. Jones, James S. Maskery, Christopher D. Thomas [email protected] School of Chemistry, Bangor University Bangor, LL57 2UW, UK. Conformational analysis of potential energy hypersurfaces is a laborious task even with recent advances in computing power. Bond counting rules (BCRs)[1] compare strengths of interatomic interactions allowing qualitative energetic predictions for specific atomic arrangements. Quantitative BCRs were developed for polyhydroxybenzoquinone dyes. Intramolecular H-bonding (with associated ring formation in QTAIM analyses) stabilizes conformations by ca. 20 kJ·mol-1, whilst H…H interactions must be avoided. The applicability the BCR approach to inorganic ring systems will be demonstrated using the [B6O7(OH)6]2- polyborate anion which contains a central trivalent “O+” atom at the junction of three rings (Figure 1). Intramolecular H-bonding stabilizes conformer A by 20 kJ·mol-1 relative to conformer B.

Figure 1. Hexaborate [B6O7(OH)6]2- structures: conformer A (middle), B (right).

Acknowledgements: We wish to thank the European Social Fund (ESF) for funding of a KESS (Knowledge Economy Skills Scholarships) PhD studentship. References: [1] (a) M. Mattesini, S.F. Matar, Int. J. Inorg. Mater., 2001, 943-957; (b) M. Mattesini, S.F. Matar, Comp. Mater. Sci., 2001, 107-119; (c) X.F. Fan, Z. Zhu, Z. X. Shen, J.L. Kuo, J. Phys. Chem. C, 2008, 15691-15696.

Poster presentation - P148

New ionic liquids containing the 2-Phosphaethynolate-anion Maximilian Jost, Lars H. Finger, Carsten von Hänisch, Jörg Sundermeyer* [email protected] Fachbereich Chemie, Philipps-Universität Marburg Hans-Meerwein-Straße 4, GER-35032, Marburg In 1992 the heavier congener of the cyanate ion the PCO--anion was first synthesized by Becker et al.[1] In recent years the chemistry of this anion has been explored, in particular by the groups of Grützmacher and Goicoechea.[2–4] The counterions of this anion are usually alkaline or alkaline earth metals, organic counterions are still unknown. Herein we present the first ionic liquids (IL) with the PCO--anion containing different organic counterions, which were prepared starting from the methylcarbonateanion, circumventing the application of highly reactive LiP(SiMe3)2. Furthermore we investigated the reactivity of those IL’s against Tris(trimethylsilyl)stibane. In the course of the reaction we could not obtain the heavier congener SbCO--anion, instead we crystallized [P(nBu)3Me]3Sb11, the first Ufosan-structure which contains a [Sb11]3- anion with organic cations.

Figure 1. Above: Schematic pathway to novel compounds containing the PCO--anion and molecular structure of C(NMe2)3PCO. Below: Molecular structure of [P(nBu)3Me]3Sb11.

References: [1] G. Becker, W. Schwarz, N. Seidler, M. Westerhausen, Z. anorg. allg. Chem. 1992, 612, 72–82. [2] F. F. Puschmann, D. Stein, D. Heift, C. Hendriksen, Z. A. Gal, H. F. Grützmacher, H. Grützmacher, Angew. Chemie - Int. Ed. 2011, 50, 8420–8423. [3] A. R. Jupp, J. M. Goicoechea, J. Am. Chem. Soc. 2013, 135, 19131–19134. [4] A. R. Jupp, J. M. Goicoechea, Angew. Chemie - Int. Ed. 2013, 52, 10064–10067.

Poster presentation - P149

Generation of a tripodal Schiff-base metalloligand Francisco M. García-Valle, Tomás Cuenca, Vanessa Tabernero, Jesús Cano* and Marta E. G. Mosquera* [email protected] Departamento de Química Orgánica y Química Inorgánica, University of Alcalá Facultad de Farmacia, Ctra. Madrid-Barcelona (Autovía A2) Km. 33,600,Campus Universitario, 28871-Alcala de Henares, Madrid. Spain. Schiff-base compounds are very attractive ligand precursors due to their steric and electronic properties and their amenability to modification. Their straightforward preparation and easy purification make them very popular candidates for the preparation of a wide variety of metallic compounds.[1] However, not many heterometallic derivatives containing main group metals have been described with Schiff-base ligands, even though homometallic derivatives show very interesting reactivities. In particular, aluminium or alkali Schiff-base compounds are very active in catalytic polymerization processes,[2] and also in other activation reactions such as nucleophilic additions to carbonyl compounds.[3] In our group, we are interested in generating a new class of Schiff-base heterometallic complexes using main group metals. These studies have allowed us to isolate new compounds and the formation of a novel aluminate tripodal metalloligand (Figure 1). The behaviour of these species in polymerization processes and activation of small molecules is being analysed.

Figure 1. Tripodal aluminate metalloligand.

References: [1] (a) Makio, H.; Terao, H.; Iwashita, A.; Fujita, T. Chem. Rev. 2011, 111, 2363 ; (b) García-Valle, F. M.; Estivill, R.; Gallegos, C.; Cuenca, T.; Mosquera, M. E. G.; Tabernero, V.; Cano, J. Organometallics 2015, 34, 477. [2] (a) Zhang, J.; Jian, C.; Gao, Y.; Wang, L.; Tang, N.; Wu, J. Inorg. Chem. 2012, 51, 13380 ; (b) Zhang, J.; Xiong, J.; Sun, Y.; Tang, N.; Wu, J. Macromolecules 2014, 47, 7789. (c) Nomura, N.; Ishii, R.; Yamamoto, Y.; Kondo, T. Chem.-Eur. J. 2007, 13, 4433. [3] Ternel, J.; Agbossou-Niedercorn, F.; Gauvin, R. M. Dalton Trans. 2014, 43, 4530.

Poster presentation - P150

PREPARATION OF CONDUCTING PANI GRAFT POLYMERS Nazmiye Kilic,(a) E. Busra Celebia,b, Adem Kilic, Serkan Yesilot, Ferda Hacivelioglu(a)* [email protected] Gebze Technical University PK.141, 41400, Gebze, KOCAELI Since the discovery of doped polyacetylene (PA) as a conducting polymer in 1977[1] it has been found that only a few polymers, polythiophene (PTh), polypyrrole (PPy) and polyaniline (PANI) are stable enough under environmental conditions to be incorporated in practical applications. In these important conducting polymers, PANI has many advantages over other conducting polymers. PANI is thermally stable and can be easily synthesized chemically and electrochemically via oxidative polymerization in various organic solvents and/or in aqueous media[2]. However, similar to other pi-conjugated polymers, the application range of PANI, is limited due to its insolubility and infusibility. Therefore, in order to improve the solubility and induce fusibility of the stiff chain of PANI, various procedures have been proposed. Polyphosphazenes are inorganic polymers comprised of a backbone of alternating P and N atoms with two side groups linked to each phosphorus atom. Although the structure of these polymers are written as a sequence of alternating single and double bonds, in fact the bonding is not of the classical pπ-pπ type as in their counterparts in classical organic conjugated polymers. The most attractive properties of the polyphosphazenes are the stability of the inorganic chain to oxidation, reduction, and photochemical, or thermal bond cleavage, provided appropriate selection of side groups are attached to phosphorus atom [3]. In this study we investigated preparation of PANI grafted poly[bis(3-methylphenoxy(sulfonicacid)]phosphazene (PSAP) via chemical oxidation. The resulting polymers have been characterized by FT-IR, 1H and 31 P NMR and thermal, surface, optical and conductivity properties of the resulting graft polymers have been investigated.

Acknowledgements: This research was supported by The Scientific and Technological Research Council of Turkey [TUBITAK, Project no: 114Z314]. We also thank to COST action Smart Inorganic Polymers (SIPs, www.sips-cost.org ). References: [1] Shirakawa H, Louis EJ, MacDiarmid AG, Chiang CK, Heeger AJ., Chem Commun., 1977, 578–80. [2] Syed AA, Dinesan MK. Talanta, 1991; 38, 815–37. [3] Allcock H R. Chemistry and applications of polyphosphazenes, Wiley-Interscience, NY, 2003.

Poster presentation - P151

Methanol Synthesis in Silico. Quantumchemical Calculations on a Cu4Zn3O3 Picomodel Daniel Himmel, Marc Jäger, Ingo Krossing* [email protected] Institut für Anorganische und Analytische Chemie, Albert-Ludwigs-Universität Freiburg Albertstr. 1, D-79106 Freiburg im Breisgau Methanol can be synthesized from hydrogen and carbon dioxide (or carbon monoxide) on a copper-zinc oxide catalyst at temperatures above 200-250 °C and pressures of 30-100 bar. Despite many speculations about possible intermediates, the mechanism is poorly understood. We constructed a Cu4Zn3O3 cluster as smallestpossible approximation for the catalyst bulk phase which is small enough for highly accurate ab inito calculations. Using high level quantumchemical methods, possible intermediate species were screened and pathways constructed from them.

Figure 1. One possible catalytic circle. Gibbs energies were calculated with [DLPNOCCSD(T)/A(wC)VDZ – MP2/A(wC)VDZ + MP2/A(wC)VQZ] //B3LYP-D3(BJ)/def2TZVPP

Poster presentation - P152

Low valent Pentaaryl Cyclopentadienyl Fe, Co and Ni Complexes Uttam Chakraborty,(a) Niels van Velzen,(b) Sjoerd Harder,(b) and Robert Wolf*(a) [email protected] (a). Institute of Inorganic Chemistry, University of Regensburg, D-93040 Regensburg (b) Chair of Inorganic and Organometallic Chemistry, University of ErlangenNürnberg, D-91058 Erlangen Pentaaryl cyclopentadienyl ligands are attractive ligands for low-valent 3d metal ions, because they can confer substantial kinetic stabilization due to their steric bulk and promise to be less strongly electron donating than related alkyl-substituted derivatives.[1,2] However, their use can be hampered by the ready formation of the pentaaryl cyclopentadienyl radical.[2a,3,4] Here, we describe the synthesis and reactivity of complexes of general formula [CpBMBr]2 (M = Fe, Co, Ni, CpB = C5(C6H4-4-Et)5). Treatment of CpBK with [FeBr2(THF)2], CoBr2 and [NiBr2(DME)] affords [CpBFeBr]2 (1), [CpBCoBr]2 (2) and [CpBNiBr]2 (3), respectively. Dimeric 1-3 display halide-bridged solid-state molecular structures and feature a high-spin configuration for the metal atoms. The reaction of [CpBNiBr]2 (3) with Ga(NacnacDipp) followed by the addition of KC8 leads to the Ni(I) complex 4, while the direct reaction of 3 with KC8 generates a “Cp(b)Ni(I)” source which can be trapped with several substrates, e.g. N-heterocyclic carbenes, S8 or TEMPO, leading to the complexes 5-7 (Scheme 1).

Scheme 1. Synthesis of complexes 1–7. References: [1] a) W. Kläui, L. Ramacher, Angew. Chem. Int. Ed. Engl. 1986, 25, 97-98; b) H. Schumann, A. Lentz, R. Weimann, J. Pickardt, Angew. Chem. Int. Ed. Engl. 1994, 33, 1731-1733; c) C. Ruspic, J. R. Moss, M. Schürmann, S. Harder, Angew. Chem. Int. Ed. 2008, 47, 2121-2126.; d) L. D. Field, C. M. Lindall, A. F. Masters, G. K. B. Clentsmith, Coord. Chem. Rev. 2011, 255,1733-1790. [2] examples: a) H. Sitzmann, T. Dezember, W. Kaim, F. Baumann, D. Stalke, J. Kärcher, E. Dormann, H. Winter, C. Wachter, M. Kelemen, Angew. Chem. Int. Ed. 1996, 35, 2872-2875; b) M. D. Walter, J. Grunenberg, P. S. White, Chem. Sci. 2011, 2, 2120-2130; c) M. D. Walter, P. S. White, Inorg. Chem. 2012, 51, 11860-11872; d) H. Sitzmann, F. H. Köhler, et al. Organometallics 2013, 32, 6298-6305 [3] J.- . Thépot, C. apinte, J. Organomet. Chem. 2002, 656, 146-155. [4] S. Heinl, S. Reisinger, C. Schwarzmaier, M. Bodensteiner, M. Scheer, Angew. Chem. Int. Ed. 2014, 53, 7639-7642.

Poster presentation - P153

Reactions and characteristics of a cationic Ni(I)-Complex Miriam Schwab, Daniel Himmel, Melanie Wernet, Philippe Weis, Andreas Peter, Ingo Krossing* [email protected] Institut für Anorganische und Analytische Chemie, Freiburger Materialforschungszentrum (FMF) Stefan-Meier-Str. 21, GER-79104, Freiburg Weakly coordinating anions (WCAs) are often used to stabilize high reactive cations. The single negative charge of WCAs, which is delocalized over a large surface, leads to only little interactions between the anion and the associated cation.[1] One of these anions is the perfluoro-tert-butoxy aluminate which provides a cationic [NiI(cod)2]+ species (cod = 1,5-cyclooctadiene) as [Al(ORF)4]– (RF= C(CF3)3) salt. With a d9electron configuration Ni(I) is a very unstable species which usually needs strong σdonating ligands with for example phosphor and nitrogen donor atoms.[2] [NiI(cod)2][Al(ORF)4] (1) as a powder indicates no oxygen or air sensitivity, whereas a solution in CH2Cl2 shows a changed signal in EPR spectrum when oxygen is present. Reaction tests with mono- or bidentate phosphine ligands resulted in ligand exchanges (Figure 1), whereas utilization of more coordinating solvents like THF lead to disproportionation to Ni0 and [Ni(THF)6][Al(ORF)4]2.

Figure 1. Ligand exchange of 1 with PPh3 and dppp (1,3-bis(diphenylphosphino)propane). Acknowledgements: This work was supported by the Freiburger Materialforschungszentrum of the University of Freiburg (FMF) and funded by the ERC project UniChem References: [1] I. Krossing, I. Raabe, Angew. Chem. 2004, 116, 2116–2142. [2] a) M. Vogt, B. de Bruin, H. Berke, M. Trincado, H. Grützmacher, Chem. Sci. 2011, 2, 723–727; b) D. C. Bradley, M. B. Hursthouse, R. J. Smallwood, A. J. Welch, J. Chem. Soc., Chem. Commun. 1972, 872–873; c) A. Gleizes, M. Dartiguenave, Y. Dartiguenave, J. Galy, H. F. Klein, J. Am. Chem. Soc. 1977, 99, 5187–5189; d) L. Sacconi, P. Dapporto, P. Stoppioni, J. Am. Chem. Soc. 1975, 97, 5595– 5596.

Poster presentation - P154

The reactivity of [(C10H15)Fe(5-P5)] and [(C5H2tBu3)Ni(3-P3)] Eric Mädl, Manfred Scheer* [email protected] Institute of Inorganic Chemistry, University of Regensburg Universitätsstr. 31, GER-93053, Regensburg The long known pentaphosphaferrocene [Cp*Fe(5-P5)] shows a divers reactivity pattern. Whereas in the past the reactions with various organometallic reagents have been broadly investigated,[1] its use as a building block in coordination and supramolecular chemistry was recently discovered by our group.[2] Moreover, first reactivity with nucleophiles[3] and reducing agents[4] was recently reported by us. We report here on the reactivity of pentaphosphaferrocene [Cp*Fe(5-P5)] towards LiNMe2, yielding a rare P5-envelope structural motif and the subsequent reactions with transition metal halides of the type [Cp'''MX]2 (M = Fe, Co; X = Cl, Br). Furthermore, the reactivity of [Cp'''Ni(3-P3)] towards NaNH2, forming an anionic triple-decker, is described, which can be subsequently oxidized.

Scheme 1. The different reactivity patterns of pentaphosphaferrocene and [Cp'''Ni(3-P3)].

References: [1] O. J. Scherer, Acc. Chem. Res. 1999, 32, 751–762. [2] M. Scheer, Dalton Trans. 2008, 4372-4386. [3] M. V. Butovskii, G. Balázs, M. Bodensteiner, E. V. Peresypkina, A. V. Virovets, M. Scheer, Angew. Chem. 2013, 125, 3045-3049. [4] E. Mädl, M. V. Butovskii, G. Balázs, E. V. Peresypkina, A. V. Virovets, M. Seidl, M. Scheer, Angew. Chem. Int. Ed. 2014, 53, 7643-7646.

Poster presentation - P155

Dinuclear Iron and Ruthenium Complexes Containing Naphthalene as a Bridging Ligand Dirk Herrmann, Jennifer Malberg and Robert Wolf* [email protected] University of Regensburg, Institute of Inorganic Chemistry Universitätsstr. 31, 93053 Regensburg Germany Bimetallic complexes with polyaromatic hydrocarbon ligands may display a variable degree of electronic coupling between the metal centers, depending on the nature of the bridging ligand.[1] Various polyarene ligands have been used in the past, but binuclear complexes containing the simplest polyarene naphthalene are scarce.[2] Here, we describe an investigation of the properties of naphthalene as a bridging ligand in dinuclear iron and ruthenium complexes, including heterobimetallic derivatives. We report the synthesis and characterization of a series of compounds of type [CpRM(µ‑naphthalene)M'Cp*] (CpRM = Cp*Fe, Cp'Fe, and Cp*Ru; Cp*M' = Cp*Fe, and Cp*Ru; Cp* = C5Me5, Cp' = C5H2tBu3).[3] The molecular structures feature an anti-facial arrangement where the metal cations are bound to opposite sides of the naphthalene molecule. An investigation of the redox properties (cyclic voltammetry and UV-vis spectroelectrochemistry) in conjunction with DFT calculations reveals the strong electronic coupling between the metal atoms in these complexes. Monocations [CpRM(µ-naphthalene)MCp*]+ were isolated by oxidation of the neutral species and characterized by X-ray crystallography and spectroscopic techniques. These cations can be classified as borderline class II / class III compounds in case of the FeFe and FeRu species, while the RuRu cation [Cp*Ru(µC10H8)RuCp*]+ appears to be a class III compound with full charge delocalization.[4]

References: [1] reviews: a) A. Ceccon et. al., Coord. Chem. Rev. 2004, 248, 683-724; b) D. Astruc, Acc. Chem. Res. 1997, 30, 383-391; c) D. S. Perekalin, A. R. Kudinov, Coord. Chem. Rev. 2014, 276, 153-173. [2] a) W. H. Morrison, E. Y. Ho, D. N. Hendrickson, J. Am. Chem. Soc. 1974, 96, 3603-3608; b) K. Jonas, Pure Appl. Chem. 1990, 62, 1169-1174; c) U. Kölle, M. H. Wang, Organometallics 1990, 9, 195-198; d) H. Salembier, R. M. Chin et. al., Organometallics 2012, 31, 4838-4848. [3] a) E.-M. Schnöckelborg, F. Hartl, T. Langer, R. Pöttgen, R. Wolf, Eur. J. Inorg. Chem. 2012, 16321638; b) J. Malberg, R. Wolf et. al., Organometallics 2013, 32, 6040-6052. [4] M. B. Robin, P. Day, Adv. Inorg. Chem. Radiochem. 1967, 10, 247-422. [5] D. Herrmann, E. Lupton, F. Hartl, R. Wolf, manuscript in preparation.

Poster presentation - P156

Transformations of Small Inorganic Molecules by Low-valent Transition Metalate Anions and Transition Metal Radicals Robert Wolf,* Uttam Chakraborty,(a) Stefan Pelties,(a) Niels van Velzen,(b) and Sjoerd Harder(b) [email protected] (a) University of Regensburg, Institute of Inorganic Chemistry, D-93040 Regensburg; (b) Chair of Inorganic and Organometallic Chemistry, University ErlangenNürnberg, Egerlandstraße 1, D-91058 Erlangen This talk will discuss the chemistry of new low-oxidation state cyclopentadienyl iron, cobalt and nickel complexes. The first part will describe the synthesis of Nheterocyclic carbene-stabilized cyclopentadienylnickel(I) radicals.[1] The complexes have a modular structure that allows the modification of their steric and electronic properties. The reactivity of these new nickel(I) radicals with radical traps such as white phosphorus and elemental sulfur will be examined. The second part will discuss the chemistry of new pentarylcyclopentadienyl complexes.[2] These uncommon Cp derivatives are able to stabilize compounds with unusual structures and reactivity patterns as illustrated for example by the synthesis of the first tetraphosphacyclobutadiene iron complex, [CpAr5Fe(cyclo-P4)]- and the dinuclear hexasulfide [(CpAr5Ni)2(µ-S6)] (Figure 1).

Figure 1. Reactivity of new cyclopentadienyl iron and nickel complexes.

Acknowledgements: We thank Moritz Modl and Prof. Manfred Scheer (University of Regensburg) for collaborating on CpBig chemistry. References: [1] S. Pelties, D. Herrmann, B. de Bruin, F. Hartl, R. Wolf, Chem. Commun. 2014, 50, 7014-7016. [2] a) W. Kläui, L. Ramacher, Angew. Chem. Int. Ed. Engl. 1986, 25, 97-98; b) H. Schumann, A. Lentz, R. Weimann, J. Pickardt, Angew. Chem. Int. Ed. Engl. 1994, 33, 1731-1733; c) C. Ruspic, J. R. Moss, M. Schürmann, S. Harder, Angew. Chem. Int. Ed. 2008, 47, 2121-2126.; d) L. D. Field, C. M. Lindall, A. F. Masters, G. K. B. Clentsmith, Coord. Chem. Rev. 2011, 255,1733-1790.

Poster presentation - P157

Coordination chemistry of new di-/monoanionic ferrocene-based di/phosphido chelate ligands Sandra Hitzel, Clemens Bruhn, Ulrich Siemeling [email protected] Institute of Chemistry, University of Kassel Heinrich-Plett-Str. 40, GER-34132, Kassel The 1,1´-difunctionalisation of ferrocene with donor atoms like nitrogen and phosphorus is of great interest in organometallic and coordination chemistry, in particular in terms of catalytic applications.1 The resulting ligands can be categorized as either neutral (L,L type, for example the well-known dppf ligand) or dianionic (X,X type). During our investigations, we were able to isolate monoanionic (L,X type) intermediates. Whereas N,N’-difunctionalised ferrocene frameworks of the type [Fe{C5H4(NHR)}2] (1H2) and their diamido chelate ligand form [Fe{C5H4(NR)}2]2(1) are well established, the phosphorus homologues of 1H2are completely underdeveloped. This fact is surprising in view of the great current interest in transition metal phosphido complexes.2 The only representative known to date is [Fe{C5H4(PHPh)}2] (2H2a).3 We will present a range of new [Fe{C5H4(PHR)}2] derivatives (2H2b-e) bearing substituents of different steric and electronic characteristics. Furthermore, results concerning their deprotonation and their coordination behaviour e.g. towards nickel will be shown.

Figure 1. Diaminoferrocenes of type 1H2 and their deprotonated form 1. Diphosphinoferrocenes of type 2H2 and their chelating coordination modes towards nickel.

References: [1] Reviews: (a) Ferrocenes, eds. Togni, A., Hayashi, T. VCH, Weinheim, 1995 (b) Siemeling, U., Auch, T.-C. Chem. Soc. Rev. 2005, 34, 584 [2] Rosenberg, L. Coord. Chem. Rev. 2012, 256, 606 [3] Lane, E. M., Chapp, T. W., Hughes, R. P., Glueck, D. S., Feland, B. C., Bernard, G. M., Wasylishen, R. E., Rheingold, A. L. Inorg. Chem. 2010, 49, 3950

Poster presentation - P158

Applications of the five-membered ring products of cyclometalation reactions as OLEDs Iwao Omae [email protected] Omae Research Laboratories 335-23, Mizuno, Sayama, Saitama, 350 -1317, Japan Cyclometalation reactions producing five-membered ring products progress regioselectively and extremely easily by using many kinds of metal compounds with various kinds of substrates because the produced five-membered ring compounds are the most stable as compared with the other ring compounds such as four- and sixmembered rings [1-3]. Those massive five-membered ring products are applied in many fields such as catalysts, OLEDs, pharmaceuticals, dye-sensitized solar calls, carbon dioxide utilization, sensors, and so on. The summary of these applications are already reported as a monograph in 2014 [3]. This research describes mainly on recent developments in OLEDs. The OLED Handbook in 2014 reported that the largest uses of OLEDs are not in TVs but mobile phones, digital cameras, wearable devices, notebook PCs and tablets. The total annual sales of OLED displays exceeded $10 billion in 2013 [4]. The presence of a high field strength ligand such as N-heterocyclic carbene (NHC) iridium compounds, in the compounds giving rise high energy emissions, and consequently leading desired blue color emission needed for the OLED applications. Neutral two-electron donors show pronounced s-donor ability with little to no p-back bonding. Due to their strong s-electron-donating properties, NHC ligands usually form strong bonds with most metal centers and are therefore highly resistant towards decomposition. Thus, Luminescence Technology Corp. (OLED maker) also manufactured mostly these carbene compounds as the OLED products. Hence, these NHC iridium compounds such as imidazole-type carbene compounds, are mostly expected to be the cyclometalated iridium compounds of great promise as blue color emitting compounds for the OLED devices. The other compounds used as the OLED devices are NCN tridentate compounds, 2phenylpyridine compounds, 2-phenylpyridine fluorinated compounds, phenyltriazole compounds, 2,3'-bipyridine compounds and triphenyltriazole dendrimers.

References: 1. I. Omae, Chem. Rev. , 1979, 79, 287. 2. I. Omae, Organometallic Intramolecular- coordination Compounds, Elsevier, Amsterdam, 1986. 3. I. Omae, Cyclometalation Reactions: Five-Membered Ring Products as Universal Reagents, Springer, Tokyo, 2014. 4. R. Mertens, A Guide to OLED Technology, Industry & Market, 2014 Ed.

Poster presentation - P159

Carbolithiation vs. Deprotonation: Control of the Reaction Behavior of Allylamines towards Alkyllithium Reagents Ulrike Kroesen, Lena Knauer, Carsten Strohmann* [email protected] Faculty of Chemistry and Chemical Biology, TU Dortmund University Otto-Hahn-Str. 6, GER-44227, Dortmund Lithiation reactions represent a manifold and important type of reaction in organic and metalorganic synthesis. They allow the creation of highly reactive molecular building blocks and further reactions with electrophiles. One challenge is the synthesis via competing deprotonation and carbolithiation and the understanding of metastable metalated species. In the presented results the main focus lies on allylamines and their metalation using alkyllithium reagents as well as the Schlosser’s Base, directed by the formation of inorganic ring intermediates.[1] Allylamines show high potential in the use as homoenolate equivalents and enable the synthesis of otherwise inaccessible building blocks, which are particulary significant in the synthesis of pharmaceuticals and natural products.[2] The focus of this research lies on the influence of the metalating reagent – particularly the alkali metal (Li, Na, K) – and on the structure and stability of the synthesized compounds as well as the study of the regio- and stereochemistry of the reactions depending on the alkyllithium reagent and the solvent.

Figure 1. Carbolithiation vs. Deprotonation.

Acknowledgements: We are grateful to the Deutsche Forschungsgemeinschaft (DFG) and the Fonds der Chemischen Industrie (FCI) for financial support. References: [1] (a) M. Schlosser, Pure Appl. Chem. 1988, 60, 1 27 b) . ochmann, J. Pospíšil, D. Tetrahedron Lett. 1966, 2, 257. [2] H. Ahlbrecht, G. Boche, K. Harms, M. Marsch, H. Sommer, Chem. Ber. 1990, 123, 1853.

ím,

Poster presentation - P160

Polyarene Metalates as Precatalysts for Hydrogenations: Scope and Mechanism Philipp Büschelberger,(a) Dominik Gärtner,(b) Babak Razaei Rad,(a) Axel Jacobi von Wangelin (b)* and Robert Wolf (a)* [email protected] University of Regensburg, (a) Institute of Inorganic Chemistry, and (b) Institute of Organic Chemistry Universitätsstraße 31, D-93040 Regensburg Catalytic hydrogenations constitute one of the most important operations for the conversion of raw chemicals and the synthesis of fine chemicals and pharmaceuticals.[1] In addition to the well-developed noble metal catalysts, there is great interest in developing new catalysts based on more abundant first-row transition metals.[2] We recently found that the bis(anthracene)cobaltate 1 is an active precatalyst for the hydrogenation of alkenes, ketones and imines under mild conditions.[3] Surprisingly, the iron analogue 2 is significantly less active. The poster will compare the catalytic properties of 1 and 2 with a series of related alkene and arene complexes 3–7, which feature iron and cobalt in different oxidation states. Several of these complexes were found to be catalytically active, albeit none parallels the properties of 1. Moreover, we will address the nature of the catalytically active species. The results of NMR-monitoring studies and selective catalyst poisoning experiments will be presented.

References: [1] a) B. Plietker, Iron Catalysis in Organic Chemistry: Reactions and Applications, John Wiley & Sons, 2008; b) B. Plietker, M. Beller, Iron Catalysis: Fundamentals and Applications, Springer, 2011. [2] M. S. Holzwarth, B. Plietker, ChemCatChem 2013, 5, 1650–1679. [3] a) W. W. Brennessel, V. G. Young, Jr., J. E. Ellis, Angew. Chem. Int. Ed. 2002, 41, 1211–1215; b) D. Gärtner, A. Welther, B. Razaei Rad, R. Wolf, A. Jacobi von Wangelin, Angew. Chem. Int. Ed. 2014, 53, 3722–3726; c) W. W. Brennessel, R. E. Jilek, J. E. Ellis, Angew. Chem. Int. Ed. 2007, 46, 6132–6136.

Poster presentation - P161

Studies on heteroleptic Cp*Be-R compounds Dominik Naglav, Briac Tobey, Stephan Schulz* [email protected] Faculty of Chemistry, University of Duisburg-Essen Universitatsstr. 5-7, GER-45141, Essen The authors present extensive studies on several hitherto unknown heteroleptic Cp*BeX compounds (Cp* = pentamethylcyclopentadienyl / X = F [1], Cl [2], Br [3], I [4]) focussing on solid state structures, theoretical investigations and 9Be-NMR. We present the solid state structures of 2, 3 and 4 and their solvent depending 9Be-NMR shifts. They crystallize isostructurally as colorless crystals in the monoclinic space group P21/c with two independent molecules in the unit cell. To get more details about the bonding situations in these complexes we performed ELF (electron localization function) and LOL (localized orbital localization), as well as NBO (natural bond orbital) analysis on the geometry optimized structures from DFT calculations (def2-TZVPP/B3LYP) including Cp*BeF. The ELF figures and NBO charges show a highly polarized Be-center in the complexes, whereas the LOL analyses demonstrate an increasing covalent character of the Be-X bond with higher atomic numbers of the halide. The charge on the Be center decreases with the increase of the covalency of the beryllium halide bond.

Figure 1. 2D ELF plots of [1] to [4] of in the C(ring)-Be-X-plane and 3D LOL plots of 1 to 4 with v = 0.53.

References: [1] D. Naglav, A. Neumann, B. Tobey, D. Bläser, C. Wölper, S. Schulz, Organomet., manuscript in preparation.

Poster presentation - P162

Calcium Hydride Catalyzed Highly 1,2-Selective Pyridine Hydrosilylation Heiko Bauer,(a) Julia Intemann,(b) Jürgen Pahl,(a) Sjoerd Hardera,* [email protected] a: Department of Inorganic and Organometallic Chemistry, Friedrich-Alexander University Erlangen-Nürnberg, Egerlandstraße 1, 91058 Erlangen, Germany b: Stratingh Institute for Chemistry, Nijenborgh 4, 9747AG Groningen, The Netherlands Early work by Ashby et al. showed that addition of MgH2to pyridine gives a mixture of 1,2- and 1,4-dihydropyridides (DHP), but subsequent heating led to exclusive isomerization to the 1,4-derivative.[1-2] Similarly, dearomatization of pyridine by bdiketiminate magnesium hydride intermediate, yields pure 1,4-DHP after heating.[3],[4] We recently found that a coupled β-ketiminate magnesium hydride complex reacts with pyridine to give exclusively the 1,2-DHP product, with less than 10% conversion to 1,4-DHP after excessive heating.[5] Unfortunately, under a catalytic regime only mixtures of 1,2- and 1,4-products could be found. Reaction of the calcium hydride complex (DIPPnacnac-CaH·THF)2 with pyridine is much faster and more selective than that of the corresponding magnesium hydride complexes. With a range of pyridine, picoline and quinoline substrates, exclusive transfer of the hydride ligand to the 2-position is observed and also at higher temperatures no 1,2→1, isomerization is found. The product DIPPnacnac-Ca(1,2-dihydropyridide)·(pyridine) is not stable towards ligand exchange into homoleptic calcium complexes and could not be isolated, but the crystal structure of the homoleptic product from calcium hydride reduction of isoquinoline, Ca(1,2-dihydroisoquinolide)2·(isoquinoline)4, has been determined. This unusual 1,2-selectivity in the dearomatization of pyridines was utilized in catalysis. Whereas hydroboration of pyridine with pinacol borane with a calcium hydride catalyst gave only minor conversion, the hydrosilylation of pyridine and quinolines with PhSiH3yields exclusively 1,2-dihydropyridine and 1,2dihydroquinoline silanes with 80-90% conversion. These calcium complexes represent the first catalysts for the 1,2-selective hydrosilylation of pyridines.

References: [1] E. C. Ashby, A. B. Goel, J. Am. Chem. Soc. 1977, 99, 310 [2] E. C. Ashby, A. B. Goel, J. Chem. Soc. Chem. Commun. 1977, 169. [3] M. S. Hill, D. J. MacDougall, M. F. Mahon, Dalton Trans. 2010, 39, 11129. [4] M. S. Hill, G. Kociok-Köhn, D. J. MacDougall, M. F. Mahon, C. Weetman, Dalton Trans. 2011, 40, 12500. [5] J. Intemann, M. Lutz, S. Harder, Organometallics 2014, 33, 5722.

Poster presentation - P163

Synthesis and reactivity of an unprecedented cationic Mg βdiketiminate complex Jürgen Pahl, Tom Stennett, Harmen Zijlstra, Sjoerd Harder* [email protected] Department of Chemistry and Pharmacy, Friedrich-Alexander Universität ErlangenNürnberg, Egerlandstraße 1, 91058, Erlangen, Germany Cationic complexes of group 3 and 4 metals are well known; they represent models of active species or potential intermediates in, for instance, the polymerization of αolefins.[1] By contrast, occurrences of alkaline earth metal cationic complexes remain rather scarce[2], especially ones employing β-diketiminate ligand systems.[3] Besides the β-diketiminate ligand, these complexes rely on strongly coordinating solvents such as pyridine and tetrahydrofuran for stabilization. Abstraction of a butyl group from DIPPNacnacMgBu in aromatic solvents affords a cationic Mg complex containing a coordinated arene molecule (1, Figure 1). Up until now the coordination of unpolar solvents like benzene and toluene to alkaline earth metals could only be observed for select barium compounds.[3]

Figure 1. Synthesis of a cationic β-diketiminate magnesium complex.

References: [1] M. Bochmann, Organometallics 2010, 29, 4711-4740. [2] a) M. G. Cushion, P. Mountford, Chem. Commun., 2011, 47, 2276–2278; b) B. J. Ireland, C. A. Wheaton, P. G. Hayes, Organometallics, 2010, 29, 1079-1084; c) C. Lichtenberg, P. Jochmann, T. P. Spaniol, J. Okuda, Angew. Chem. Int. Ed. 2011, 50, 5753 –5756. [3] B. Liu, V. Dorcet, L. Maron, J. Carpentier, Y. Sarazin, Eur. J. Inorg. Chem. 2012, 3023–3031 [4] L. Bonomo, E. Solari, R. Scopelliti, C. Floriani, Chem. Eur. J., 2001, 7, 1322-1332.

Poster presentation - P164

Regioselective deprotonation of N-heterocyclic molecules using ßdiketiminate stabilized magnesium bases Laia Davin, Alberto Hernán-Gómez, Eva Hevia* [email protected] WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde 295 Cathedral Street, G1 1XL, Glasgow, UK Despite their prevalence in many pharmaceuticals and natural products, the regioselective metallation of N-heterocyclic molecules such as diazines or pyridines using polar organometallic reagents still remains an important challenge in synthesis.[1] This is primarily due to the low stability of the generated metallated intermediates which undergo fast decomposition at room temperature.[2] In this poster, we present our findings in developing novel magnesium reagents supported by βdiketiminate ligands as a new synthetic strategy for the regioselective deprotonation of sensitive N-heterocyclic molecules. Using kinetically activated amide base 1,[3] it is possible to selectively alpha-magnesiate a range of substrates, including Nmethylbenzimidazole, N-methyl triazole and pyrazine at room temperature (Figure 1a). Structural studies on the metallated intermediates (Figure 1b) provide important clues that help to rationalise the stability of these species in solution.

Figure 1: a) Selective C2 metallation of pyrazine. b) Molecular structure of 2.

References: [1] F. Chevallier, F. Mongin, Chem. Soc. Rev. 2008, 37, 595. [2] S. E. Baillie, V. L. Blair, D. C. Blakemore, D. Hay, A. R. Kennedy, D. C. Pryde, E. Hevia, Chem. Commun. 2012, 48, 1985. [3] S. E. Baillie, V. L. Blair, T. D. Bradley, W. Clegg, J. Cowan, R. W. Harrington, A. Hernán-Gómez, A. R. Kennedy, Z. Livingstone, E. Hevia, Chem. Sci., 2013, 4, 1895.

Poster presentation - P165

Towards new concepts for bond activation using an iron-PBP-pincer complex Lisa Vondung, Nicolas Frank, Dr. Robert Langer* [email protected] Fachbereich Chemie, Philipps-Universität Hans-Meerwein-Straße 4, 35032 Marburg In the past, efficient homogeneous catalysts relied heavily on precious metals such as ruthenium, platinum and palladium. An increasing demand for these metals has lead to the wish of governments and industry to replace precious metal catalysts with more abundant and ideally non-toxic metals. One highly attractive alternative is iron.[1] Unfortunately, the established concepts can’t be easily transferred from ruthenium to iron, as iron often prefers one electron redox processes over two electron processes.[2] Thus the development of new concepts is required. The new iron-PBP-pincer complex 2 was obtained via formal BH3 insertion in a Fe-P bond (complex 1, see fig. 1)[3] and subsequent rearrangement under CO atmosphere. The second reaction represents a rare example of B-H activation of a BR4 species. Complexes 1 and 2 were characterized by single crystal x-ray diffraction and NMR. NOESY-NMR experiments revealed an exchange between the Fe-H and B-H in complex 2, which was further investigated by temperature dependent NMR experiments and DFT calculations. The Fe0L4-fragment, which is anticipated as an intermediate in the exchange process has a high potential for bond activation.[4]

Figure 1. Synthesis of iron-PBP-pincer complex 2.

References: [1] S. Enthaler, K. Junge, M. Beller, Angew. Chem. Int. Ed. 2008, 47, 3317-3321. [2] P. J. Chirik, K. Wieghardt, Science 2010, 327, 794-795. [3] N. Frank, K. Hanau, K. Flosdorf, R. Langer, Dalton Trans. 2013, 42, 11252-11261. [4] (a) H.-F. Klein, S. Camadanli, R. Beck, D. Leukel, U. Flörke, Angew. Chem. Int. Ed. 2005, 44, 975-977. (b) R. Birk, H. Berke, G. Huttner, L. Zsolnai, Chem. Ber. 1988, 121, 1557-1564.

Poster presentation - P166

Trigonal to tetrahedral transitions in Cu(I) six-membered inorganic true heterocycles Michal Horni, Radim Binar and Marek Necas [email protected] Department of Chemistry, Faculty of Science, Masaryk University Kotlarska 267/2, 611 37 Brno A series of six-membered Cu(I) true heterocycles[1] was prepared from reactions of [Cu(PPh3)2]NO3 with Ph2P(S)-N-C(O)R {R = (CH2)3CH3, C6H5, C6H4F, C6H4Cl} ligands. The synthesized compounds were characterized by 31P NMR spectroscopy and single crystal X-ray diffraction. According to NMR spectroscopy, most of the prepared complexes should contain copper in tetrahedral coordination environment. After crystallization from CH2Cl2/hexane system, the complexes with PNC ligands possessing dissimilar halogen substituent (position and type) on benzene ring show different copper coordination polyhedra (Figure). Quantum chemical calculations are undertaken to reveal thermodynamic and kinetic phenomena determining copper atom coordination geometries.

Figure 1. Trigonal and tetrahedral Cu(I) complexes.

Acknowledgements: To Mr. Babiak and X-ray Diffraction and Bio-SAXS Core Facility, CEITEC MU. European Regional Development Fund (CZ.1.05/1.1.00/02.0068). References: [1] Birdsall, D. J.; Green, J.; Ly, Q. T.; Novosad, J.; Necas, M.; Slawin, A. M. Z.; Woollins, J. D.; Zak, Z., Eur. J. Inorg. Chem., 1999, 1445 – 1452.

Poster presentation - P167

The Transmetalation Strategy to Heterometallic Gold Clusters Mathies V. Evers,(a) Arik Puls,(a) Christian Gemel,(a) Yuichi Negishi,(b) Roland A. Fischer(a)* [email protected] (a) Chair of Inorganic Chemistry II, Ruhr-University Bochum Universitätsstr. 150, 44801, Bochum (Germany) (b) Department of Applied Chemistry, Faculty of Science, Tokyo University of Science Shinjuku-ku, Tokyo, 162-8601 (Japan) Gold clusters are prominent materials in nanoscience. They exhibit high reactivity, catalytic activity and interesting optical properties, which are strongly dependent on size, structure and capping ligands. Every cluster atom is crucial to the chemical and physical features and thus, doping has evolved as a tool for the fine-tuning of the properties. However, the established wet chemical synthesis (co-reduction) of heterometallic clusters is challenging and limited in scope, especially if the nature of the two metals is very different. Recently, we discovered a novel transmetalation strategy to yield multiply metal-doped gold clusters: [M(AuPMe3)11(AuCl)]3+ (M@Au12, M = Ni, Pd, Pt) and [Mo(AuPMe3)8(GaCl2)3(GaCl)]+ (Mo@Au8Ga4) were prepared from [M(GaCp*)4] and [Mo(GaCp*)6], respectively, by reaction with Cl– Au–PMe3.[1] In expanding this concept we now discovered a unique access to the first all-isonitrile-capped heterometallic gold clusters of the general formula {[AuaMb]L12}2+ (L = CNtBu; M = Pd, Pt; a + b = 13). As shown by single-crystal XRD and high resolution mass spectroscopy, their molecular structure consists of an icosahedral metal cage with one central atom M and the other heterometal atoms M distributed over the icosahedral shell. Interestingly, the electron count cve = 6 of the obtained examples {[Au8M5]L12}2+ does not fit the Jellium superatom counting rules for clusters.[2] The synthesis, spectroscopic features as well as molecular and electronic structures will be discussed.

Figure 1. Synthesis of {[Au8M5](CNtBu)12}2+ (M = Pd, Pt) and mass spectrum for M = Pt.

References: [1] A. Puls, P. Jerabek, W. Kurashige, M. Förster, M. Molon, T. Bollermann, M. Winter, C. Gemel, Y. Negishi, G. Frenking, R. A. Fischer, Angew. Chem. Int. Ed., 2014, 53, 4327-4331. [2] H. Häkkinen, Chem Soc. Rev., 2008, 37, 1847-1859.

Poster presentation - P168

Chiral Potassium Derivatives bearing Ligands of Natural Origin María Fernández-Millán, Ghaita Chahboun, Jesús Cano, Tomás Cuenca and Marta E. G. Mosquera [email protected] Departamento de Química Orgánica y Química Inorgánica, University of Alcalá Ctra. Madrid-Barcelona Km. 33,600, E-28805, Alcalá de Henares (Madrid) In this century, there has been a significant focus on the use of renewable feedstock as raw materials to prepare chemicals. Renewable feedstock derived from plant-based materials has also the advantage of presenting low toxicity. Moreover, the use of this kind of natural occurring compounds is of particular interest as it permits to take advantage of the pre-functionalization in those species. In this context, terpenoids are molecules of great interest since they are starting materials of natural origin coming from cheap non-food crops. In addition, they are chiral and commercially available as enantiomerically pure products. As well, the presence of instaurations in their structures gives the opportunity of performing further functionalization in a stereoselective way.[1] However, despite the great potential of terpene derivatives as ligands, the number of coordination compounds with this type of species is low, especially with main group metals. In our research group, we are interested in the preparation of alkali derivatives with these ligands. This work has led us to the synthesis of tetrametallic potassium chiral compounds very active in lactide polymerization processes.

Figure 1. Terpene-based derivative.

References: [1] A. J. D. Silvestre, A. Gandini en „Monomers, Polymers and Composites from Renewable Resources“ Elsevier, 2008, 17-38. K. Yao, C. Tang, Macromolecules 2013, 46, 1689-1712. R. Noyori, M. Kitamura, Angew. Chem.-Int. Edit. Engl. 1991, 49; K. R. Jain, W. A. Herrmann, F. E. Kuhn, Coord Chem. Rev. 2008, 252, 556.

Poster presentation - P169

PTFE (“Teflon”) Sealing Ring for greaseless conical Glass Joint and for All-Glass-Syringe Dietmar Glindemann, Uwe Glindemann [email protected] Glindemann Polymer Technologies Goettinger Bogen 15, 06126 Halle There is a prejudice that PTFE (“Teflon”) is too inelastic to be a hermetic sealant for greaseless conical joints. Therefore, teaching books [1,2] recommend threaded or flanged “O-ring joints” for hermetic manipulation of air- and moisture sensitive chemicals if joint grease is no option. Here we show[3] that the common ground conical glass joint can be sealed relatively hermetic and at low cost with a narrow flat PTFE sealing ring (less than 1 mm wide and 0.1 mm thick, weight only 5 mg PTFE). The sealing ring is high-vacuum tight (air leakage rate 10-8… 10-6 mBar*Liter/sec), solvent tight (loss of ethyl acetate out of containers: 0.1 mg/day) and resistant to fluctuation of temperature (freezing-thawing-heating cycles). The reusable PTFE sealing ring prevents stuck joints, is thin enough to be used with all joint clamps and is fixed elastically (without groove) on the glass joint. We demonstrate also that the common all-glass-syringe (1-100 mL) becomes gastight by a similar exchangeable sealing ring (PTFE) in a groove of the glass piston.[4]

Figure 1. Left: PTFE-sealing ring fixed elastic (no groove necessary). Middle: Sealing ring intransparent without pressure. Right: Sealing ring transparent under sealing pressure. Far right: A similar PTFE ring and a piston groove make an allglass-syringe.

References: [1] D.F. Shriver, M.A. Drezdzon, The Manipulation of Air-Sensitive Compounds, Wiley: New York, 1986; p. 153-159. [2] R.J. Errington, Advanced Practical Inorganic and Metalorganic Chemistry, Blackie; London, 1997, p. 37-39. [3] D. Glindemann, U. Glindemann, Fusion, 2001, 48, 29. [4] D. Glindemann, All-glass syringe. Utility patent, DE 20 2006 020 555.1 (2009.03.05.).

Poster presentation - P170

Synthesis of Functional Inorganic Materials starting from Metal Alkoxide and Metal Thiolate Precursors Johannes Schläfer, Ufuk Atamtürk, Aida Jamil, Ralf Müller, Sanjay Mathur* [email protected] Institute of Inorganic Chemistry, University of Cologne Greinstraße 6, D-50939 Cologne, Germany Chemical synthesis of nanostructured materials starting from well-defined precursors offers a high controllability over morphology as well as elemental composition and purity. In order to meet the high requirements put on material performance progressive processing techniques such as chemical vapor deposition were established providing an elegant way to chemically assemble nanostructured phases starting from molecular building units. Hereby, a drastically reduction of reaction parameters during synthesis could be achieved by deploying single-source precursors providing a high homogeneity already on a molecular level and exhibiting consistent physicochemical properties such as vapor pressure or decomposition behavior. Metal alkoxides and metal thiolates are a versatile class of precursors due to their unique structural diversity, intrinsic propensity to hydrolysis, predefined M-E-bonds (E = O, S) and defined decomposition mechanism. Here, we report the synthesis and characterization of several homo- and heterometallic complexes and their deployment as single-source precursor using different material synthesis approaches.1,2

Figure 1. SnO2 nanowires prepared by thermal CVD using alkoxide precursor [Sn(OtBu)4].

Acknowledgements: The authors gratefully acknowledge the financial support provided by the University of Cologne. References: 1 R. Müller, F. Hernandez-Ramirez, H. Shen, H. Du, W. Mader, S. Mathur, Chem. Mater. 2012, 24, 4028-4035. 2 J. Schläfer, S. Stucky, W. Tyrra, S. Mathur, Inorg. Chem. 2013, 52, 4002-4010.

Poster presentation - P171

Precursor Synthesis for the Generation of Fluorine-dope SnO2 Nanomaterials Lisa Czympiel1, Corinna Hegemann1, Tim Heidemann1, Jean-Marius Lekeu1, Jan Podhorsky2, Jiri Pinkas2, Sanjay Mathur1, * [email protected] 1Institute of Inorganic Chemistry, University of Cologne Greinstr. 6, D-50939, Cologne; 2Institute of Chemistry, Masaryk University Kamenice 753/5, 625 00 Brno Fluorine-doped tin-dioxide (FTO) is a widely studied material for photo-catalysis, in optical sensors or as thin film transparent electrode. The Research Group of Professor Mathur is constantly investigating new precursors for a molecule-based approach to nanomaterials by liquid-phase as well as gas-phase techniques. In the course of our ongoing efforts towards suitable precursors we are investigating the properties of heteroaryl alkenols as chelating ligands for various metals.[1] Through the direct oxidation of tin (II) derivatives[2] as well as very atom economic solvent free melt reactions dihalogeno tin(IV) bis(heteroarylalkenolates) are easily accessible. Furthermore to optimize the tin to oxygen ratio for the later nanomaterial new heteroleptic alkoxo Sn(IV) complexes were synthesized and characterized. These compounds are interesting synthons for further chemical modifications or materials syntheses.

Figure 1. Set of investigated potential molecular precursors for the synthesis of FTO.

Acknowledgements: The authors thank Dr. Wieland Tyrra for useful discussions and Dr. Stefan Stucky for assistance with the X-ray crystal structure determination. References: [1] (a) . Brückmann, W. Tyrra, S. Stucky, S. Mathur, Inorg. Chem. 2012, 51, 3 − 2 (b) . Appel, R. Fiz, W. Tyrra, S. Mathur, Dalton Trans. 2012, 41, 19 1−1990 (c) . Appel, J. Leduc, C. L. Webster, J. W. Ziller, W. J. Evans, S. Mathur, Angew. Chem. Int. Ed. 2015, 54, 2209–2213; (d) L. Czympiel, J. Pfrommer, W. Tyrra, M. Schäfer, S. Mathur, Inorg. Chem. 2015, 54, 25-37. [2] (a) I. Giebelhaus, R. Müller, W. Tyrra, I. Pantenburg, T. Fischer, S. Mathur, Inorg. Chim. Acta 2011, 372, 3 0−3 (b) T. Heidemann, S. Mathur, Eur. J. Inorg. Chem. 2014, 506–510.

Poster presentation - P172

Exploring the Chemistry of Ternary Heterometallic Alkoxides Corinna Hegemann, Tim Heidemann, Sanjay Mathur* [email protected] 1Institute of Inorganic Chemistry, University of Cologne Greinstr. 6, D-50939, Cologne The bimetallic nonaalkoxo unit, {M2(OPri9)}-, is a promising building block to rationally construct new heterobimetallic alkoxides[1] whereas no report is available on the structural characterization of the {Ce2(OPri)9}- unit in the solid state. This along with the interest for mixed-metal cerium containing ceramics prompted our research work in heterobi- and trimetallic metal(IV)-isopropoxides. New heterobimetallic halide isopropoxides of the general formula [IM{Ce2(OPri)9}]2(M = Cd, Ba) were successfully used as synthons to novel ternary heterometal alkoxides [{Cd(OPri)3}M{Ce2(OPri)9}]2 (M = Ba, Sr) and the monomeric i i IV i IV [{Al(OPr )4}(HOPr )Ba{M 2(OPr )9}] (M = Zr, Hf, Ce). Whereas the formation of a heterotrimetallic framework in [{Cd(OPri)3}Ba{Ce2(OPri)9}]2 starting with [ICd{Ce2(OPri)9}]2 involves the previously observed switching of cadmium and alkaline earth metal atoms, [{Al(OPri)4}(HOPri)Ba{MIV2(OPri)9}] was obtained by a straightforward salt elimination reaction between [ICd{MIV2(OPri)9}]2 and [K{Al(OPri)3}]n [{Al(OPri)4}(HOPri)Ba{MIV2(OPri)9}] represents a novel structural motif and the first example of a volatile homoleptic heterotrimetallic alkoxide containing an trivalent metal atom.

Figure 1. Formation of the heterotrimetallic framework in [{Cd(OPri)3}Ba{Ce2(OPri)9}]2.

Acknowledgements: The authors thank Dr. Wieland Tyrra for useful discussions and Dr. Ingo Pantenburg for assistance with the X-ray crystal structure determination. References: [1] a) M. Veith, S. Mathur, V. Huch, J. Chem. Soc., Dalton Trans. 1996, 12, 2485-2490; b) R. C. Mehrotra, A. Singh, Polyhedron 1998, 17, 689-704; c) M. Veith, C. Mathur, S. Mathur, V. Huch, Organometallics 1997, 16, 1292-1299; d) M. Veith, S. Mathur, V. Huch, Inorg. Chem. 1997, 36, 23912399; e) M. Veith, S. Mathur, C. Mathur, Polyhedron 1998, 17, 1005-1034; f) R. C. Mehrotra, A. Singh, S. Sogani, Chem. Rev. 1994, 94, 1643-1660; g) K. G. Caulton, L. G. Hubert-Pfalzgraf, Chem. Rev. 1990, 90, 969-995.

Poster presentation - P173

Ligand-Modulated Chemical and Structural Implications in Aluminum Heteroaryl Alkenolates Lisa Czympiel,(a) Mathias Schäfer,(b) Johannes Pfrommer,(a) Sanjay Mathur*(a) [email protected] a) Institute of Inorganic and b) Institute of Organic Chemistry, University of Cologne Greinstr. 6, D-50939, Cologne With continuing research interest and increasing technological importance of nanomaterials, particularly thin films of functional materials, the quest for new metal−organic compounds, enabling a controlled synthesis of new materials has gained significant impetus in recent years. To study the mode of stabilization of the triply charged aluminum ion by aromatic groups and heteroatoms like nitrogen, oxygen, and sulfur, we report on a series of aluminum chelate complexes with six different heteroaryl alkenolate anions. The chelating ability of the NAr−CH−C(Rf)−OH backbone of the ligands and the stability of the resulting sixmembered ring offer an interesting option to limit the oligomerization of metal complexes while simultaneously enhancing the volatility by incorporating an perfluoralkyl-unit. Synthesis and characterization (gas phase, solution, and solid-state) of a series of homoleptic and heteroleptic four‑, five- and six-fold coordinated heteroaryl-alkenolato aluminum complexes were performed to demonstrate the delicate interplay of structural and chemical influences of ligands in the design of new precursors for chemical vapor deposition.

Figure 1. Correlation of coordination numbers of metal atoms in Al complexes with their chemical shifts in 27Al NMR spectra. Acknowledgements: Authors acknowledge G. Berden and J. Oomens for IRMPD-measurements, and A.J.H.M. Meijer for theoretical calculations of the compounds which allowed the elucidation of gasphase structures. References: 1 (a) L. Czympiel, J. Pfrommer, W. Tyrra, M. Schäfer, S. Mathur, Inorg. Chem., 2015, 54, 25 - 37; (b) L. Brückmann, W. Tyrra, S. Mathur, G. Berden, J. Oomens, A.J.H.M. Meijer, M. Schäfer, ChemPhysChem, 2012, 13, 2037 - 2045.

Poster presentation - P174

BODIPY-Cyclophosphazene-Fullerene Triad as Heavy Atom Free Organic Triplet Photosensitizer Elif OKUTAN*, Semiha YILDIRIM, Serkan YESILOT, Adem KILIC [email protected] Department of Chemistry, Gebze Technical University TR-41400, KOCAELI Triplet photosensitizers have attracted much attention, because of their applications in photovoltaics, photodynamic therapy (PDT) and the triplet-triplet annihilation photon upconversions.[1] Generally the triplet photosensitizers are transition metal complexes or the iodo/ bromo containing organic chromophores in which the heavy atom effect facilitates ISC. Recently organic triplet photosensitizers based on BODIPY have been reported.[2] But it is not always convenient to prepare iodinated/brominated organic chromophore since the ISC property of these chromophores cannot be guaranteed. It is still a challenge to design a heavy-atom-free organic triplet photosensitizer. In this study, the synthesis and photophysical properties of new triad BODIPYcyclophosphazene-fullerene (Figure 1.) in which BODIPY moieties are connected to an cyclophosphazene core, which acts as an thermally stable carrier/router and is further linked to three C60 units. This model utilizes visible light absorbing three cis directed BODIPY derivatives as antennas and cis directed fullerenes as spin convertor in the same molecule. This molecular design can trigger the strong absorption of visible light and very long-lived triplet excited states and may be used as heavy atom free organic triplet photosentisitizers.

Acknowledgements: The authors would like to thank the Scientific and Technical Research Council of Turkey for financial support TUBITAK (Grant 114Z763 ) References: [1] W. Wu, H. Guo, W. Wu, S. Ji, J. Zhao, J. Org. Chem.,2011, 76, 70 −70 . [2] S. Ji, W. Wu , W. Wu, H. Guo, J. Zhao, Angew. Chem., Int. Ed., 2011, 50, 1 2 −1 29.

Poster presentation - P175

List of Participants Dr. Tomohiro Agou Institute for Chemical Research, Kyoto University 6110011 Kyoto Japan

Mr. Frederik Aicher 72119 Ammerbuch Germany

Ms. Nazmiye Akbay Kilic Gebze Technical University 41400 Kocaeli Turkey

Ms. Mansura Akter 53117 Bonn Germany

Ms. Lena Albers Universität Oldenburg 26129 Oldenburg Germany

Prof. Simon Aldridge University of Oxford OX1 3QR Oxford United Kingdom

Prof. Chris Allen University of Vermont 05405 Burlington United States

Martina Amann University of Regensburg 93053 Regensburg Germany

Mr. Naoki Ando Nagoya University 4648602 Nagoya Japan

Mr. Marius Arz University of Bonn 53121 Bonn Germany

Bernhard Baars University of Bonn 53123 Bonn Germany

Katharina Baier University of Regensburg 93053 Regensburg Germany

Mr. Matthew Baker ETH Zürich 8049 Zürich Switzerland

Prof. Maravanji Balakrishna I I T BOMBAY 400076 Mumbai India

Dr. Gábor Balázs University of Regensburg 93053 Regensburg Germany

Mr. Hung Banh Ruhr-Universität Bochum, AC II 44801 Bochum Germany

List of Participants

Mr. Peter Bartoš Masaryk University 971 01 Prievidza Slovakia

Dr. Heiko Bauer Friedrich-Alexander University ErlangenNürnberg 91058 Erlangen Germany

Dr. Thomas Baumgartner University of Calgary, Department of Chemistry T2N 1N4 Calgary Canada

Dr. Michael Beckett Bangor University LL57 2UW Bangor United Kingdom

Prof. Jens Beckmann Universität Bremen 28334 Bremen Germany

Ms. Imtiaz Begum University of Bonn 53119 Bonn Germany

Mr. Lukas Belter 40468 Düsseldorf Germany

Dr. Zoltán Benkö Budapest University of Technology and Economics 1111 Budapest Hungary

Prof. Louise Berben University of California Davis 95616 Davis United States

Prof. Guy Bertrand UC San Diego CA 92093 San Diego United States

Prof. Serap Beşli Gebze Technical University 41400 OCAE İ Turkey

Prof. Holger Bettinger Institute for Organic Chemistry, University Tuebingen 72076 Tuebingen Germany

Dr. Ilya Bezkishko IOPC KSC RAS 42088 Kazan Russia

Mr. Michal Bílek University od Pardubice 532 10 Pardubice Czech Republic

Mr. Justin Frank Binder Department of Chemistry and Biochemistry, University of Windsor N9B 3P4 Windsor Canada

Mr. Markus Blum University of Stuttgart 73614 Schorndorf Germany

Dr. Michael Bodensteiner University of Regensburg 93053 Regensburg Germany

Prof. René Boeré University of Lethbridge T1K3M4 Lethbridge Canada

List of Participants

Dr. Tobias Boettcher Albert-Ludwigs Universität Freiburg 79104 Freiburg Germany

Mr. Jaap E. Borger VU University Amsterdam 1081HV Amsterdam Netherlands

Mr. Stefan Borucki University of Kassel 34132 Kassel Germany

Mr. Jiří Böserle Univerzita Pardubice 53210 Pardubice Czech Republic

Dr. Didier Bourissou Paul Sabatier University 31062 Toulouse France

Jens Braese University of Regensburg 93053 Regensburg Germany

Helena Brake University of Regensburg 93053 Regensburg Germany

Prof. Holger Braunschweig Julius-Maximilians-Universität Würzburg 97074 Würzburg Germany

Prof. Frank Breher Karlsruhe Institute of Technology (KIT), Institute of Inorganic Chemistry 76131 Karlsruhe Germany

Dr. Nora Breit Technische Universität Berlin 10623 Berlin Germany

Mr. Jonas Bresien University of Rostock 18059 Rostock Germany

Dr. Lies Broeckaert Universität Marburg 35032 Marburg Germany

Natalie Brüll Philipps-Universität Marburg 35039 Marburg Germany

Prof. Neil Burford University of Victoria V8W 3V6 Victoria Canada

Mr. Philipp Büschelberger University of Regensburg 93040 Regensburg Germany

Dr. Jesus Campos Manzano University of Oxford OX1 3QR Oxford United Kingdom

Ms. Elif Busra Celebi Yildiz Technical University 34220 istanbul Turkey

Dr. Uttam Chakraborty University of Regensburg 93055 Regensburg Germany

List of Participants

Dr. Yuk Chi Chan Nanyang Technological University 637371 Singapore Singapore

Ms. Bronte Charette R2J 0B4 Winnipeg Canada

Prof. Ching-Wen Chiu National Taiwan University 10617 Taipai Taiwan

Prof. Tristram Chivers University of Calgary T2N 1N4 Calgary, Alberta Canada

Mr. Tomas Chlupaty University of Pardubice 53210 Pardubice Czech Republic

Prof. John Corrigan The University of Western Ontario N6A5B7 London Canada

Dr. Michael Cowley School of Chemistry, University of Edinburgh EH9 3FJ Edinburgh United Kingdom

Prof. Christopher C. Cummins Massachusetts Institute of Technology MA 02139 Cambridge United States

Dr. Derya Davarci Gebze Technical University 41400 OCAE İ Turkey

Dr. Andrew Davies Bangor University LL57 2UW Bangor United Kingdom

Laia Davin University of Strathclyde G1 1XL Glasgow United Kingdom

Prof. Stefanie Dehnen FB Chemie, Philipps-Universität Marburg 35039 Marburg Germany

Dr. Fabian Dielmann University of Münster 48149 Münster Germany

Ms. Katharina Dilchert Ruhr-Universität Bochum 44809 Bochum Germany

Dr. Adinarayana Doddi Technische Universität Braunschweig 38106 Braunschweig Germany

Mr. Carsten Donsbach Philipps-University Marburg D-35032 Marburg Germany

Mr. Eike Dornsiepen Philipps-Universität Marburg 35039 Marburg Germany

Dr. Libor Dostál University of Pardubice 53210 Pardubice Czech Republic

List of Participants

Prof. Ralf Dr. Steudel 14055 Berlin Germany

Dr. Jonathan Dube Max Planck Institut für Kohlenforschung 45470 Mülheim an der ruhr Germany

Luis Duetsch University of Regensburg 93053 Regensburg Germany

Ms. Klara Edel University of Tübingen 72076 Tübingen Germany

Ms. Jessica Edrich 71069 Sindelfingen Germany

Dr. Andreas Ehlers Vrije Univeriteit 1081HV Amsterdam Netherlands

Mr. Carsten Eisenhut Technische Universität Berlin 10623 Berlin Germany

Dr. Mehdi Elsayed Moussa University of Regensburg 93049 Regensburg Germany

Mr. Armin Rainer Eulenstein Philipps-Universität Marburg 35032 Marburg Germany

Mr. Mathies Evers Ruhr-University Bochum 45468 Mülheim an der Ruhr Germany

Dr. Rosalyn Falconer University of Bristol BS8 1TS Bristol United Kingdom

Mr. Jan Faßbender 53639 Königswinter Germany

Prof. Thomas Fässler Technische Universität München 85748 Garching Germany

Dr. María Fernández Millán University of Alcalá 28871 Alcalá de Henares (Madrid) Spain

Prof. Roland C. Fischer TU Graz 8010 Graz Austria

Martin Fleischmann University of Regensburg 93051 Regensburg Germany

Dr. Daniel Franz Technische Universität Berlin 10623 Berlin Germany

Dr. Kerstin Freitag Ruhr-Universität Bochum 44801 Bochum Germany

List of Participants

Prof. Francois Gabbai Texas A&M University TX 77843 College Station United States

Dr. Olga Gapurenko Institute of Physical and Organic Chemistry, Southern Federal University 344090 Rostov on Don Russia

Mr. Francisco Miguel García-Valle University of Alcalá 28871 Alcalá de Henares Spain

Prof. Derek P. Gates University of British Columbia V6T 1Z1 Vancouver Canada

Eugenie Geringer Philipps-Universität Marburg 35032 Marburg Germany

Mr. Priyabrata Ghana University of Bonn 53121 Bonn Germany

Dr. Robert Gilliard ETH Zurich 8093 Zurich Switzerland

Dr. Glen Briand Mount Allison University E4L1G8 Sackville, New Brunswick Canada

Dr. Dietmar Glindemann Glindemann PTFE Sealing Rings D-06126 Halle Germany

Prof. Jose Goicoechea University of Oxford OX1 3TA Oxford United Kingdom

Mr. Christopher Golz TU Dortmund, Anorganische Chemie 44227 Dortmund Germany

Dr. Marta Elena Gonzalez Mosquera Universidad de Alcala 28805 Alcala de Henares Spain

Mr. Paul Gray University of Victoria V8P4R2 Victoria Canada

Ms. Christa Grogger TU Graz 8010 Graz Austria

Mr. Henning Großekappenberg Universität Oldenburg 26129 Oldenburg Germany

Mr. Peter Grüninger University of Tübingen 72762 Reutlingen Germany

Prof. Hansjörg Grützmacher ETH Zürich 8093 Zürich Switzerland

Prof. Dietrich Gudat University of Stuttgart 70550 Stuttgart Germany

List of Participants

Mr. Lukas Guggolz Philipps-Universität Marburg 35043 Marburg Germany

Mr. Michael Haas Institute of Inorganic Chemistry 8010 Graz Austria

Prof. Ferda Hacivelioglu Gebze Technical University 41400 Kocaeli Turkey

Ms. Katharina Hanau Philipps-Universität Marburg 35032 Marburg Germany

Ms. Róża Hamera University of Lodz, Faculty of Chemistry, Department of Organic and Applied Chemistry 91-403 Łódź Poland Ms. Kerstin Hansen Technische Universität Berlin 10623 Berlin Germany

Prof. Sjoerd Harder University Erlangen-Nürnberg 91058 Erlangen Germany

Ms. Khatera Hazin UBC V3J7G8 Burnaby Canada

Dr. Corinna Hegemann University of Cologne 50939 Cologne Germany

Oliver Hegen University of Regensburg 93053 Regensburg Germany

Mr. Tim Heidemann 50937 Köln Germany

Dr. Dominikus Heift LPCNO, INSA Toulouse 31077 Toulouse France

Claudia Heindl University of Regensburg 93051 Regensburg Germany

Dr. Johanna Heine Philipps-Universität Marburg 35043 Marburg Germany

Mr. Martin Hejda University od Pardubice 53210 Pardubice Czech Republic

Dr. Holger Helten RWTH Aachen University 52056 Aachen Germany

Mr. Dirk Herrmann University of Regensburg 93053 Regensburg Germany

Prof. Eva Hevia University of Strathclyde G1 1XQ Glasgow United Kingdom

List of Participants

Prof. Evamarie Hey-Hawkins Universität Leipzig 04103 Leipzig Germany

Dr. Daniel Himmel Krossing Group, Freiburg 79098 Freiburg im Breisgau Germany

Mr. Alexander Hinz Universität Rostock 18059 Rostock Germany

Sandra Hitzel University of Kassel 34132 Kassel Germany

Mr. Michal Horni Masaryk University 61137 Brno Czech Republic

Mr. Emanuel Hupf Universität Bremen 28359 Bremen Germany

Prof. Takeaki Iwamoto Tohoku University 9808578 Sendai Japan

Dr. Roman Jambor University of Pardubice 53210 Pardubice Czech Republic

Ms. Aida Jamil University of Cologne 50939 cologne Germany

Dr. Brian Johnson Wiley-VCH 69469 Weinheim Germany

Prof. Cameron Jones Monash University VIC 3800 Clayton Australia

Charlotte Jones Bangor University LL57 2UW Bangor United Kingdom

Mr. Maximilian Jost Philipps-Universität Marburg 35032 Marburg Germany

Mr. Philip Junker University of Bonn 53115 Bonn Germany

Mr. Andrew Jupp University of Oxford OX13PN Oxford United Kingdom

Dr. Titel Jurca University of Bristol BS8 1TS Bristol United Kingdom

Prof. Klaus Jurkschat Fakultät für Chemie und Chemische Biologie,TU Dortmund 44221 Dortmund Germany

Tobias Kahoun University of Regensburg 93053 Regensburg Germany

List of Participants

Prof. Wolfgang Kaim University of Stuttgart 70550 Stuttgart Germany

Mr. Manuel Kapitein Philipps-Universität Marburg 35043 Marburg Germany

Mr. Denis Kargin Universität Kassel 34471 Volkmarsen Germany

Mr. Surendar Karwasara Indian Institute of Technology Delhi 110016 Delhi India

Mr. Ralf Kather Universität Bremen 28359 Bremen Germany

Mr. Dominik Keiper Philipps-Universität Marburg 35032 Marburg Germany

Mr. Zsolt Kelemen Budapest University of Technology and Economics H-1111 Budapest Hungary

Dr. Shabana Khan Indian Institute For Science Education And Research Pune, India 411008 PUNE India

Ms. Sabrina Khoo Nanyang Technological University 419593 Singapore Singapore

Karin Kilgert University of Regensburg 93053 Regensburg Germany

Mr. Andreas Kirchmeier University of Kassel 34132 Kassel Germany

Ms. Melina Klein University of Bonn 53121 Bonn Germany

Dr. Evgeny Kolychev University of Oxford OX1 3TA Oxford United Kingdom

Prof. Sergey Konchenko Nikolaev Institute of Inorganic Chemistry SB RAS 630090 Novosibirsk Russia

David Konieczny University of Regensburg 93053 Regensburg Germany

Dr. Jari Konu University of Jyväskylä FI-40014 Jyväskylä Finland

Stephanie Kosnik University of Windsor, Chemistry & Biochemistry N9G2L7 Windsor Canada

Barbara Krämer University of Regensburg 93053 Regensburg Germany

List of Participants

Mr. Kilian Krebs University of Tübingen 72076 Tübingen Germany

Dr. Robert Kretschmer University of Regensburg 93053 Regensburg Germany

Ms. Ulrike Kroesen TU Dortmund, Anorganische Chemie 44227 Dortmund Germany

Prof. Ingo Krossing Uni Freiburg 79104 Freiburg i. Br. Germany

Mr. Selva Kumar 642005 coimbatore India

Dr. Arvind Kumar Gupta NDHU 97401 Hualien Taiwan

Mr. Mahendra Kumar Sharma Iit Delhi, India 110016 NEW DELHI India

Dr. Oleksandr Kysliak University of Tübingen 72074 Tübingen Germany

Mr. René Labbow University of Rostock 18059 Rostock Germany

Giuliano Lassandro University of Regensburg 93053 Regensburg Germany

Dr. Richard Layfield School of Chemistry, The University of Manchester M13 9PL Manchester United Kingdom

Lucia-Myongwon Lee McMaster University L8S4M1 Hamilton Canada

Dr. Vladimir LEE University of Tsukuba 305-8571 Tsukuba Japan

Mr. Otfried Lemp Philipps-Universität Marburg 35032 Marburg Germany

Dr. Christophe Lescop Institut des Sciences Chimiques de Rennes 35042 Rennes France

Ms. Eliza Leusmann Philipps-Universität Marburg 35032 Marburg Germany

Mr. Niels Lichtenberger Philipps University of Marburg 35043 Marburg Germany

Dr. H. Bernhard Linden Linden CMS GmbH 28844 Weyhe Germany

List of Participants

Mr. Mathias Linden Linden CMS GmbH 28844 Weyhe Germany

Dr. Felicitas Lips University of Muenster 48149 Münster Germany

Prof. Chen-Wei Liu National Dong Hwa University 97401 Hualien Taiwan

Mr. Siu Kwan Lo University of Oxford OX1 3TA Oxford United Kingdom

Ms. Alicia López Andarias Organisch-Chemisches Institut 69115 Heidelberg Germany

Ms. Kathrin Louven TU Dortmund, Anorganische Chemie 44227 Dortmund Germany

Petra Lugauer University of Regensburg 93053 Regensburg Germany

Mr. Dennis Lutters Universität Oldenburg 26129 Oldenburg Germany

Dr. Charles Macdonald University of Windsor, Chemistry & Biochemistry N9B 3P4 Windsor, Ontario Canada

Eric Mädl University of Regensburg 93051 Regensburg Germany

Dr. Alexander Makarov Novosibirsk Institute Of Organic Chemistry 630090 Novosibirsk Russia

Dr. Payal Malik Institut für Anorganische Chemie, Uni-Bonn D-53121 Bonn Germany

Prof. Ian Manners University of Bristol BS8 1TS Bristol United Kingdom

Christian Marquardt University of Regensburg 93053 Regensurg Germany

Mr. David Martin CNRS Université Joseph Fourier BP53 38041 Grenoble cedex 9 France

Prof. Pradeep Mathur I.I.T. Indore 452020 Indore India

Dr. Rebecca Melen Cardiff University CF10 3AT Cardiff United Kingdom

Daniela Meyer University of Regensburg 93053 Regensburg Germany

List of Participants

Mr. Stefan Mitzinger Philipps-Universität Marburg 35043 Marburg Germany

Prof. Grzegorz Mloston Faculty of Chemistry, University of Lodz 91-403 Lodz Poland

Mr. Dennis Mo 40591 Duesseldorf Germany

Moritz Modl University of Regensburg 93053 Regensburg Germany

Dr. Heather Montgomery Royal Society of Chemistry CB4 0WF Cambridge United Kingdom

Fabian Mueller ETH Zürich 8093 Zurich Switzerland

Julian Müller University of Regensburg 93053 Regensburg Germany

Prof. Thomas Müller CvO Universität Oldenburg 26129 Oldenburg Germany

Prof. Robert E. Mulvey University of Strathclyde G1 1XQ Glasgow United Kingdom

Dr. María Teresa Muñoz-Fernández University Of Alcalá 28871 Alcalá De Henares (Madrid) Spain

Ms. Cristina Murcia García University of Bonn 53123 Bonn Germany

Prof. Ramaswamy Murugavel 400076 Mumbai India

Ms. Ceylan Mutlu Gebze Technical University 41400 Kocaeli Turkey

Mr. Koichi Nagata Kyoto university 611-0011 Uji city Japan

Mr. Dominik Naglav 45141 Essen Germany

Mr. David Nieder Saarland University 66125 Saarbrücken-Dudweiler Germany

Mr. Miroslav Novák University od Pardubice 53210 Pardubice Czech Republic

Isabell Nußbruch Philipps-Universität Marburg 35032 Marburg Germany

List of Participants

Prof. Laszlo Nyulaszi Budapest University of Technology and Economics H-1111 Budapest Hungary

Mr. Tatsumi Ochiai Technische Universität Berlin 10623 Berlin Germany

Mr. Jan Oetzel University of Kassel 34132 Kassel Germany

Dr. Elif OKUTAN Gebze Technical University 41400 KOCAELI Turkey

Dr. Roman Olejník University of Pardubice CZ 532 10 Pardubice Czech Republic

Prof. Iwao Omae Omae Research Laboratories 350-1317 Sayama, Saitama Japan

Ms. Isabell Omlor Saarland University 66280 Sulzbach Germany

Dr. Timo Ott 47169 Duisburg Germany

Mr. Jürgen Pahl FAU Erlangen-Nürnberg 91058 Erlangen Germany

Dr. Eugenia Peresypkina University of Regensburg 93053 Regensburg Germany

Prof. Rudolf Pietschnig University of Kassel, Institut für Chemie und CINSaT 34132 Kassel Germany

Prof. Philip P. Power UC Davis CA 95616 Davis United States

Prof. Paul Pringle University of Bristol BS8 1TS Bristol United Kingdom

Dr. Nikolay Pushkarevsky Nikolaev Institute of inorganic chemistry 630090 Novosibirsk Russia

Dr. Boomi Shankar Ramamoorthy Indian Institute of Science Education and Research, Pune 411008 Pune India

Mr. Crispin Reinhold Universität Oldenburg 26129 Oldenburg Germany

Ms. Kirsten Reuter Philipps-Universität Marburg 35037 Marburg Germany

Mr. Tomáš Řičica University od Pardubice 53210 Pardubice Czech Republic

List of Participants

Felix Riedlberger University of Regensburg 93053 Regensburg Germany

Mr. Benjamin Ringler Philipps-Universität Marburg 35032 Marburg Germany

Mr. Niklas Rinn Philipps University Marburg 35039 Marburg Germany

Dr. Arnab Rit University of Oxford OX1 3TA Oxford United Kingdom

Prof. Jamie Ritch Department of Chemistry, The University of Winnipeg R3B 2E9 Winnipeg Canada

Prof. Eric Rivard University of Alberta AB T6G Edmonton Canada

Mr. Andrew Roberts University of Strathclyde G1 1XQ Glasgow United Kingdom

Dr. Thomas Robinson University of Oxford OX1 3TA Oxford United Kingdom

Prof. Greg Robinson University of Georgia GA 30602 Athens United States

Mr. Christian Roedl University of Regensburg 93040 Regensburg Germany

Dr. Carlos Romero-Nieto Organisch-Chemisches Institut 69120 Heidelberg Germany

Eva-Maria Rummel University of Regensburg 93053 Regensburg Germany

Reinhard Rund University of Regensburg 93053 Regensburg Germany

Dr. Chris Russell University of Bristol BS8 1TS Bristol United Kingdom

Prof. Ales Ruzicka University of Pardubice 53210 Pardubice Czech Republic

Prof. Masaichi Saito Department of Chemistry, Saitama University 338-8570 Saitama Japan

Silke Santner Philipps-Universität Marburg 35032 Marburg Germany

Prof. Takahiro Sasamori Kyoto University 611-0011 Uji, Kyoto Japan

List of Participants

Prof. Manfred Scheer University of Regensburg 93053 Regensburg Germany

Prof. David Scheschkewitz Saarland University 66125 Saarbrücken Germany

Dr. Johannes Schläfer University of Cologne 50939 Cologne Germany

Monika Schmidt University of Regensburg 93053 Regensburg Germany

Mr. Dominik Schnalzer Graz University of Technology 8042 Graz Austria

Ms. Julia Schneider University of Tübingen 72076 Tübingen Germany

Prof. Andreas Schnepf University of Tübingen 72076 Tübingen Germany

Thomas Schottenhammer University of Regensburg 93053 Regensburg Germany

Andrea Schreiner University of Regensburg 93053 Regensburg Germany

Mr. Jan Schroeder 79108 Freiburg Germany

Prof. Axel Schulz Universität Rostock 18059 Rostock Germany

Ms. Miriam Schwab University of Freiburg 79100 Freiburg Germany

Mr. Kai Schwedtmann Technische Universität Dresden 01062 Dresden Germany

Dr. Michael Seidl University of Regensburg 93051 Regensburg Germany

Andreas Seitz University of Regensburg 93053 Regensburg Germany

Dr. Nikolay Semenov Novosibirsk Institute of Organic Chemistry 630090 Novosibirsk Russia

Dr. Elif Şenkuytu Gebze Technical University 41400 Kocaeli Turkey

Kamna Sharma 400076 Mumbai India

List of Participants

Prof. Ulrich Siemeling University of Kassel 34132 Kassel Germany

Mr. Christian Sindlinger University of Tübingen 72076 Tübingen Germany

Prof. Nanhai Singh Banaras Hindu University 221005 Varanasi India

Mr. Jatinder Singh Iit Delhi, India 110016 New Delhi India

Prof. Alexandra Slawin University of St Andrews KY16 9ST St Andrews United Kingdom

Dr. Olivia Sleator Rigaku Europe TN15 6QY Sevenoaks United Kingdom

Dr. Chris Slootweg VU University Amsterdam 1081 HV Amsterdam Netherlands

Prof. Cheuk-Wai So Nanyang Technological University 637371 Singapore Singapore

Fabian Spitzer University of Regensburg 93051 Regensburg Germany

Prof. Dietmar Stalke Georg-August Universität 37077 Göttingen Germany

Andreas Stauber University of Regensburg 93053 Regensburg Germany

Dr. Tom Stennett Universität Erlangen-Nürnberg 91058 Erlangen Germany

Prof. Doug Stephan University of Toronto M5S 3H6 Toronto Canada

Prof. Rainer Streubel University of Bonn 53121 Bonn Germany

Prof. Carsten Strohmann TU Dortmund 44227 Dortmund Germany

Prof. Harald Stueger Graz University of Technology A8010 Graz Austria

Mr. Tomohiro Sugahara Institute for Chemical Research, Kyoto Univ. 611-0011 Uji, Kyoto Japan

Mr. Riccardo Suter ETH Zurich 8005 Zürich Switzerland

List of Participants

Dr. Petr Svec University of Pardubice CZ-53210 Pardubice Czech Republic

Prof. Claire Tessier University of Akron 44325-3601 Akron, Ohio United States

Dr. Günther Thiele Philipps-Universität Marburg 35043 Marburg Germany

Prof. Alexey Timoshkin St. Petersburg State University 198504 St. Petersburg Russia

Prof. Norihiro Tokitoh Institute for Chemical Research, Kyoto University 611-001 Uji, Kyoto Japan

Dr. Yasemin Tümer 78050 Karabük Turkey

Dr. Jan Turek ALGC, Department of Chemistry, Faculty of Sciences, Free University of Brussels 1050 Brussels Belgium

Prof.. Werner Uhl University of Muenster 48149 Münster Germany

Mr. Fabian Uhlemann University of Tuebingen 72147 Nehren Germany

Prof. Frank Uhlig Graz University of Technology 8010 Graz Austria

Prof. Aylin Uslu Gebze Technical University 41400 Kocaeli Turkey

Mr. Leon van der Boon VU University Amsterdam 1081 HV Amsterdam Netherlands

Prof. Ignacio Vargas-Baca McMaster University L8S 4M1 Hamilton Canada

Dr. Preeti Vashi Wiley-VCH, European Journal of Inorganic Chemistry 69469 Weinheim Germany

Valentin Vass University of Regensburg 93053 Regensburg Germany

Prof. Michael Veith Universität des Saarlandes und INM 66123 Saarbrücken Germany

Dr. Alexander Virovets University of Regensburg 93053 Regensburg Germany

Dr. Matthias Vogt Universität Bremen 28359 Bremen Germany

List of Participants

Prof. Carsten von Hänisch Philipps-Universität Marburg 35032 Marburg Germany

Ms. Lisa Vondung Philipps-Universität Marburg 35032 Marburg Germany

Mr. Jan Vrána Univerzita Pardubice 53210 Pardubice 2 Czech Republic

Ms. Iva Vránová Univerzita Pardubice 53210 Pardubice 2 Czech Republic

Prof. Rory Waterman University of Vermont 05401 Burlington United States

Mr. Jordan Waters University of Oxford OX1 3TA Oxford United Kingdom

Prof. Jan J. Weigand Technische Universität Dresden 01062 Dresde Germany

Dr. Bastian Weinert Philipps-Universität Marburg 35037 Marburg Germany

Rudolf Weinzierl University of Regensburg 93053 Regensburg Germany

Mr. Stefan Weller University of Stuttgart 74427 Fichtenberg Germany

Prof. Lars Wesemann University of Tübingen 72076 Tübingen Germany

Ms. Jana Weßing Ruhr-Universität Bochum, Lehrstuhl für Anorganische Chemie II 44801 Bochum Germany

Prof. Robert West University of Wisconsin-Madison 53706-1396 Madison United States

Mr. Philipp Willmes Saarland University 66125 Saarbrücken-Dudweiler Germany

Dr. Robert Wilson Philipps-Universität Marburg D-35032 Marburg Germany

Prof. Robert Wolf University of Regensburg D-93040 Regensburg Germany

Prof. J Derek Woollins University of St Andrews KY16 9ST St Andrews United Kingdom

Dr. Ronald Wustrack Universität Rostock 18059 Rostock Germany

List of Participants

Mr. Dhirendra Yadav 110016 new delhi India

Prof. Shigehiro Yamaguchi Nagoya University 464-8602 Nagoya Japan

Prof. Yohsuke Yamamoto Hiroshima University 739-8526 Higashi-Hiroshima Japan

Mr. Cem Burak Yildiz Saarland University 66125 Saarbrücken-Dudweiller Germany

Mr. Sivathmeehan Yogendra Technische Universität Dresden 01162 Dresden Germany

Ms. Hui Zhao Saarland University 66125 Saarbrucken Germany

Prof. Andrey Zibarev Russian Academy of Sciences, Novosibirsk Institute of Organic Chemistry 630090 Novosibirsk Russia

Harmen Zijlstra University of Erlangen-Nürnberg 91058 Erlangen Germany

List of Participants