th International Seminar for Ph. D. Students on ... · Welcome Address A very warm welcome is...

XIth International Seminar for Ph. D. Students on Organometallic and

Coordination Chemistry

April 06th – 10th 2008

Youth Hostel „Mortelgrund“ Sayda

Germany

Organizing Institutions

H. Lang W. Kläui Technische Universität

ChemnitzHeinrich-Heine-Universität

Düsseldorf

Welcome Address

A very warm welcome is expressed to all participants of the XIth International Seminar

for Ph. D. Students on Organometallic and Coordination Chemistry in Sayda. The

topic of the seminar covers all modern aspects in organometallic and metal-organic

chemistry including main-group elements.

We are very pleased to announce two plenary, seven invited, and fifty-four short

lectures, summarizing the most actual knowledge in different areas of transition metal

and main-group element chemistry in all kinds of systems, including both, theoretical

and experimental aspects. We hope that this platform will lead to fruitful and manifold

discussions and bring the different experts together in a warm and relaxed way. An

open exchange of ideas should be encouraged by all who attend this symposium.

The size of this meeting with ca. 90 attending scientists should allow to interact

between different disciplines, to promote creative collaborative studies, and of course

to stimulate further research topics in new areas in a interdisciplinary way.

We wish all participants of this meeting a very nice and pleasant stay in Sayda, in the

heart of the Erzgebirge.

Heinrich Lang Wolfgang Kläui

Organizing Committee Organizing Institutions:

• TU Chemnitz Faculty of Natural Science Institute of Chemistry

Inorganic Chemistry Strasse der Nationen 62 09111 Chemnitz Germany

• HHU Düsseldorf Department of Inorganic Chemistry

Universitätsstrasse 1 40225 Düsseldorf Germany Local Organizing Committee:

• Prof. Dr. H. Lang Tel. 0049 371 53121210 [email protected] • Prof. Dr. W. Kläui Tel. 0049 211 8112286 [email protected] • J. Ruder Tel. 0049 371 53121210 [email protected] • N. Rüffer Tel. 0049 371 53131836

[email protected] • U. Stöß Tel. 0049 371 53131330 [email protected] • S. Tripke Tel. 0049 371 53135818 [email protected]

Acknowledgements

The organizers greatfully acknowledge

EVONIK INDUSTRIES / Degussa GmbH

Henkel KGaA

Sponsoring-Ausschuss Der SolarWorld-Tochterunternehmen

Erdgas Südsachsen GmbH

TU Chemnitz

City-Management und Tourismus Chemnitz GmbH

Bergstadt Sayda

VW Zentrum Chemnitz

HypoVereinsbank Chemnitz

for the generous support of the XIth International Seminar for Ph. D. Students on Organometallic and Coordination Chemistry.

Previous Meetings

1st Regional Seminar of Ph. D. Students in Organometallic Chemistry; Merseburg, Germany, December 3, 1993; organized by Prof. Dr. K.-H. Thiele

2nd Regional Seminar of Ph. D. Students in Organometallic Chemistry; Prague, Czech Republic, December 1 – 3, 1994; organized by Dr. K Mach

3rd Regional Seminar of Ph. D. Students in Organometallic and Organophosphorus Chemistry;Heiligenstadt, Germany, April 15 – 19, 1996; organized by Prof. Dr. P. Binger and Prof. Dr. U. Zenneck

4th Regional Seminar of Ph. D. Students in Organometallic and Organophosphorus Chemistry;Polanica-Zdrój, Poland, October 5 – 9, 1997; organized by Prof. Dr. P. Sobota and Prof. Dr. A. Pietrzykowski

5th Regional Seminar of Ph. D. Students in Organometallic and Organophosphorus Chemistry;Se , Czech Republic, April 26 – 29, 1999; organized by Prof. Dr. J. Hole ek

6th Regional Seminar of Ph. D. Students in Organometallic and Organophosphorus Chemistry;Karpacz, Poland, April 9 – 13, 2000; organized by Prof. Dr. P. Sobota and Prof. Dr. A. Pietrzykowski

7th Regional Seminar of Ph. D. Students in Organometallic and Coordination Chemistry;Bad Kösen, Germany, March 3 - 7, 2002; organized by Prof. Dr. D. Steinborn and Dr. H. Schmidt

8th Regional Seminar of Ph. D. Students in Organometallic Chemistry; Hrubá Skalá, Czech Republic, September 29 – October 3, 2003; organized by Dr. K. Mach

9th Regional Seminar of Ph. D. Students in Organometallic and Organophosphorus Chemistry;Szklarska Por ba, Poland, April 10 – 14, 2005; organized by Prof. Dr. P. Sobota and Prof. Dr. A. Pietrzykowski

10th Regional Seminar of Ph. D. Students in Organometallic and Coordination Chemistry;Medlov, Czech Republic, September 17 – 22, 2006; organized by Prof. Dr. J. Hole ek and Dr. A. R ži ka

Contents

Programme

LecturesKeynote Lectures KL1, KL2

Invited Lectures IL1 - IL7

Short Lectures S1 - S54

Alphabetical List of Lecturers

Addresses of Lecturers

During the conference, e-mail messages can be received under the addresses or numbers given below:

[email protected]

website www.tu-chemnitz.de/chemie/anorg/ispsoc/

and faxes: 0049-371-531 21219

Programme

Sunday, April 06 2008

until 18:00 Welcome

18:15 - 19:15 Dinner

19:30 - 19:45 Opening RemarksVice-President for Research, Prof. Dr. Dr. Dietrich R. T. Zahn Dean, Faculty of Natural Sciences, Prof. Dr. Karl Heinz Hoffmann Prof. Dr. Heinrich Lang

Chair: H. Lang

19:45 - 20:30 P. J. Low KL1 Durham

Modern approaches to the study of “mixed-valence” compounds

20:30 Coming together

Monday, April 07 2008

07:00 - 08:00 Breakfast

Chair: U. Zenneck

08:30 - 09:05 P. Sobota IL1 Wroc aw

Metal complexes and organometallic compounds as precursors for electronic and ceramic materials. Old ligands, new tricks.

09:05 - 09:20 D. Mansfeld, T. Rüffer, H. Lang, M. Schürmann, M. Mehring S1 Chemnitz

Structural relationships in polynuclear bismuth oxo clusters

09:20 - 09:35 M. Meyer, W. Kläui S2 Düsseldorf

Water-soluble platinum clusters: Syntheses and catalytic Activity

09:35 - 09:50 I. Jipa, K. Michkova, N. Popovska, U. Zenneck S3 Erlangen

Arene iron and arene ruthenium complexes and their use for MOCVD applications

09:50 – 10:10 Coffee Break

Chair: A. Pietrzykowski

10:10 - 10:25 M. Rose, W. Böhlmann, S. Kaskel S4DresdenElement organic frameworks with high permanent porosity

10:25 - 10:40 T. Kaczorowski, J. Lewi ski, W. Bury, M. Dranka, S5 W. liwi ski, I. Justyniak, J. Lipkowski

WarsawDesign and characterization of novel chiral building blocks for the construction of functional porous materials

10:40 - 10:55 C. Schirrmacher, C. Bruhn, U. Siemelung, D. Käfer, G. Witte S6 Kassel

From supramolecular structures to intelligent surfaces

10:55 - 11:10 K. Döring, M. Zharnikov, A. Shaporenko, T. Weidner, R. Holze, S7 H. Lang

ChemnitzSelfassembled monolayers based on thiol-functionalized

transition metal complexes

11:10 - 11:25 J. Sienkiewicz, Z. Rz czy ska, A. Kula S8LublinSpectroscopic and thermal properties of lanthanide(III)

complexes with 2,2’-biphenyldicarboxylic acid

11:25 - 13:00 Lunch

Chair: H. Berke

13:00 - 13:35 D. Steinborn, M. Werner, S. Schwieger IL2 Halle (Saale)

Hydroxycarbenes in catalysis – platina- -diketones as model complexes

13:35 - 13:50 D. Bek, H. Balcar, J. Sedlá ek, J. ejka S9PragueImmobilized Ru complexes on mesoporous molecular sieves as catalysts for olefin metathesis

13:50 - 14:05 B. Eignerová, M. Kotora S10 Prague Perfluoroalkylation by cross-metathesis of alkenes

14:05 - 14:20 M. Marczewski, A. Boczkowska, M. Siekierski, A. Pietrzykowski S11 Warsaw

Non-hydrolytic route to synthesis methylalumoxanes in reaction of aliphatic dicarboxylic acids with trimethylaluminium, activity and

applications.

14:20 - 14:40 Coffee Break

Chair: M. Horacek

14:40 - 14:55 C. Ionescu, O. Walter, S. Pitter, E. Dinjus S12 Karlsruhe

Catalyst development for hydroformylation of long-chain olefins in sc CO2

14:55 - 15:10 I. B aszczyk, A. M. Trzeciak, J. J. Zió kowski S13 Wroc aw

Catalytic activity of Pd(II) complexes with triphenylphosphito ligands in Sonogashira reaction in ionic liquids media

15:10 - 15:25 F. Kessler, H. Fischer S14 Konstanz

Allenylidene complexes of palladium. Synthesis and catalytic properties

15:25 - 15:40 J. Schulz, I. Císa ová, P. Št pni ka S15 Prague New 1 -(diphenylphosphanyl)ferrocencarboxamides bearing

2-hydroxyethyl groups at the amide nitrogen

15:40 - 15:55 M. S. Szulmanowicz, A. M. Trzeciak S16 Wroc aw

Palladium complexes with NHC ligands used as catalysts of Suzuki-Miyaura reaction in green solvents

15:55 - 16:10 J. Tauchman, I. Císa ová, P Št pni ka S17 Prague

Phosphinoferrocene amides derived from glycine – synthesis, coordination properties, and catalytic utilization


Chair: K. Jurkschat

16:30 - 17:05 F. Meyer IL3 Göttingen

Bioinspired oxidation reactions with highly preorganized dicopper complexes

17:05 - 17:20 I. Domínguez, A. Corma, P. Concepción, V. Fornés, M. J. Sabater S18PragueA biopolymer as stabilizing agent of gold nanoparticles

17:20 - 17:35 N. E. Brückmann, P. C. Kunz S19 Düsseldorf

New polymer-metallodrug conjugates for cancer diagnostics

17:35 - 17:50 A. Wrona, J. Zakrzewski S20ód

Synthesis of ferrocenyl conjugates of thioanalogs of steroids and nucleosides via the Mitsunobu reaction using

N-(ethoxycarbonyl)ferrocenecarbothioamide as the pronucleophile

17:50 - 18:05 W. Huber, P. C. Kunz S21DüsseldorfImidazolylphosphanes for Medicinal Bioorganometallic Chemistry

18:30 BBQ

Tuesday, April 08 2008

07:00 - 08:00 Breakfast

Chair: G. Frenking

08:30 - 09:05 B. Marciniec IL4 Pozna

Inorganometallics and catalysis

09:05 - 09:20 M. Lama , I. Císa ová, P. Št pni ka S22 Prague

Ferrocene diphosphanes with planar chirality – ligands for enantioselective catalysis

09:20 - 09:35 T. Nerkowski, Z Janas, P. Sobota S23 Wroc aw

Vanadium complexes of the ONNO-type ligand. Synthesis, characterization and reactivity

09:35 - 09:50 K. Krauzy - Dziedzic, S. Szafert, J. Ejfler, P. Sobota S24 Wroc aw

Metal complexes with aryloxo, aminobisaryloxo and aryloxoimine ligands - synthesis and catalytic activity


Chair: J. Zakrzewski

10:10 - 10:25 C. Schreiner, R. Packheiser, B. Walfort, H. Lang S25 Chemnitz

Heteromultimetallic transition metal complexes

10:25 - 10:40 A. Dr g, J. Utko, . John, L. B. Jerzykiewicz, P. Sobota S26 Wroc aw

Unexpected titanocene cyclopentadienide/alkoxo group exchange

10:40 - 10:55 M. Klahn, P. Arndt, B. Heller, W. Baumann, A. Spannenberg, S27 U. Rosenthal Rostock

Synthesis, structures and reactions of chiral titanocene and zirconocene complexes

10:55 - 11:10 S. Peitz, T. Beweries, V. V. Burlakov, M. A. Bach, P. Arndt, S28W. Baumann, A. Spannenberg, U. Rosenthal

Rostock Unprecedented Si-C and C-H activation steps in the formation of hafnocene alkyne complexes

11:10 - 11:25 I. Kraszewska, M. Dranka, I. Justyniak, J. Lewi ski S29 Warsaw

Divergent coordination modes of zinc alkyls based on various pyrrolyl ligands

11:25 - 12:45 Lunch

13:00 Conference Excursion to Freiberg

19:00 Conference Banquet “Ritteressen”, Castle of Augustusburg

Wednesday, April 09 2008

07:00 – 08:00 Breakfast

Chair: R. Winter

08:30 - 09:05 G. Frenking IL5 Marburg

Coordination chemistry of divalent carbon(0) compounds – theoretical results and experimental challenge

09:05 - 09:20 A. C. Tagne Kuate, G. Reeske, M. Schürmann, K. Jurkschat S30 Dortmund

Complexation of sodium and potassium salts by ditopic hosts based on organotin-substituted crown ethers

09:20 - 09:35 P. Švec, Z. Pad lková, A. R ži ka S31 Pardubice C,N-chelated organotin(IV) fluorides

09:35 - 09:50 V. Deáky, M. Henn, M. Schürmann, B. Mahieu, K. Jurkschat S32 Dortmund

Intramolecularly coordinated heteroleptic stannylenes: Syntheses and structures

09:50 – 10:05 J. Martincová, R. Jambor, M. Schürmann, K. Jurkschat S33 Pardubice

Structure and reactivity of transition metal complexes containing the heteroleptic organostannylene 2,6-(Me2NCH2)2C6H3SnCl


Chair: N. Burzlaff

10:25 - 10:40 B. Mucha, J. Zakrzewski S34ód

1,1’-Diphosphaferrocenyl conjugates of aminoacid esters

10:40 - 10:55 E. Kami ska, P. Buchalski, A. Pietrzykowski S35 Warsaw

Synthesis of bimetallic complexes with nickelafluorenyl ring

10:55 - 11:10 B. Herbaczy ska, A. Pietrzykowski, L. B. Jerzykiewicz S36 Warsaw

Reaction of nickelocene with methyllithium in the presence of olefins

11:10 - 11:25 I. Ja yna, P. Sobota, Z. Janas S37 Wroc aw

Group IV and V metal complexes of the (NOSON)- and (ONNO)-type ligands; synthesis, structure and catalytic activity

11:25 - 11:40 M. Lechner, K. Decker, R. Fischer, F. Uhlig S38 Graz

1,1,2,2,3,3,4-Hepta-tbutyl-4-magnesio-chloro-tetrastanna- cyclobutane: Synthesis and reactions

11:40 - 13:00 Lunch

Chair: H. Fischer

13:00 - 13:35 P. Št pni ka IL6 Prague

The design of mixed-donor ferrocene ligands for enantionselective allylic alkylation

13:35 - 13:50 B. Dudle, H. Berke S39ZürichInvestigating the catalytic hydrogenation with rhenium(I) nitrosyl

complexes

13:50 - 14:05 Y. Jiang, C. M. Frech, O. Blacque, F. Thomas, H. Berke S40 Zürich

High-selective dehydrogenative silylation catalyzed by rhenium complexes: Reaction development and mechanistic studies

14:05 - 14:20 B. Dudziec, B. Marciniec S41 Pozna

Silylative coupling of terminal alkynes with vinylsilicon compounds catalyzed by ruthenium complexes

14:20 - 14:35 J. Walkowiak, M. Jankowska-Wajda, B. Marciniec S42PoznaNew catalytic route to boryl- and borylsilyl substituted

buta-1,3-dienes


Chair: A. R ži ka

14:55 - 15:10 M. A. Linseis, R. F. Winter S43 Regensburg

Oligonuclear ethenyl bridged styryl complexes of ruthenium: Synthesis, electrochemical and spectroeletrochemical investigation

15:10 - 15:25 M. Pichlmaier, S. Záliš, R. F. Winter S44 Regensburg

Styryl complexes of ruthenium and osmium as probes for electron transfer across multiple hydrogen bridges

15:25 - 15:40 A. Dybov, O. Blacque, T. Fox, C. Frech, H. Berke S45 Zürich Synthesis, characterization and properties investigation

of tungsten and molybdenum hydrides

15:40 - 15:55 R. Kami ski, P. led , S. Domaga a, B. Korybut-Daszkiewicz, S46 K. Wo niak Warsaw

New macrocyclic complexes of copper and nickel – on the network and charge density topologies

16:00 Hiking

19:30 Dinner

Thursday, April 10 2008

07:00 – 08:00 Breakfast

Chair: M. Mehring

08:00 - 08:35 L. Dostál IL7 Pardubice

Organoantimony and organobismuth pincer compounds

08:35 - 08:50 S. Filimon, D. Petrovic, T. K. Panda, M. Tamm S47 Braunschweig

Organometallic complexes supported by bis(imidazolin-2-imino)pyridine pincer ligand and by chiral ligand

08:50 - 09:05 N. Grzegorzek, M. Pawlicki, L. Latos-Gra y ski S48 Wroc aw

Toward synthesis of hybrid ligands – regioselective phosphination of carbaporpholactone

09:05 - 09:20 I. Simkowa, M. St pie , L. Latos-Gra y ski S49Wroc awHelical porphyrinoids: Incorporation of ferrocene subunits into

macrocyclic structures


Chair: P. Low

09:40 - 09:55 N. Fischer, L. Peters, N. Burzlaff S50 Erlangen

A new class of imidazole based N,N,O ligands: Synthesis, structure and reactivity

09:55 - 10:10 A. Trambitas, T. K. Panda, S. Randoll, T. Bannenberg, M. Tamm S51 Braunschweig

Mononuclear lanthanide and titanium imido complexes

10:10 - 10:25 A. Seifert, G. Linti S52 Heidelberg

Synthesis and structure of tetrameric gallium(I) amides

10:25 - 10:40 D. Prochowicz, W. Bury, J. Lewi ski, I. Justyniak S53 Warsaw

Synthesis and structure of alkylaluminium and alkylgallium derivatives of phthalic and phthalamic acid

10:40 - 10:55 K. Wójcik, P. Ecorchard, H. Lang, M. Mehring S54 Chemnitz

Cyclopentadienyl iron-bismuth compounds: Synthesis, structure and reactivity


Chair: W. Kläui

11:10 – 11:55 J. Zakrzewski KL2ód

Half-sandwich metallocarbonyl 1-N-imidato complexes in bioorganometallic chemistry

11:55 – 12:00 W. Kläui Düsseldorf Closing Remarks

12:00 – 13:00 Lunch

13:00 Departure

KEYNOTE LECTURES

6/4/2008 KL1 19:45 – 20:30

Modern approaches to the study of “mixed-valence” compounds

Paul J. Low

Department of Chemistry, Durham University, South Rd, Durham, DH1 3LE, UK.

Metal complexes of general form [{M}{ -bridge}{M}]. with open shell electronic structures

are the subject of a considerable degree of historical and contemporary interest. In the case of

systems where the unpaired electron can be attributed to a metal centre, the concepts of mixed

valency can be invoked, and analysis of the associated Intervalence Charge Transfer transition

in terms of the coupling between the metal centres using methods developed by Noel Hush

(and others) is appropriate.

However, as the metal, ancillary ligand and / or bridging ligand orbitals mix, the concept and

applicability of “metal centred valency” becomes increasingly inappropriate and new

treatments and descriptions of the underlying electronic structure are necessary. Equally, in

cases where redox-active or “non-innocent” ligands are present, electrochemical and

spectroscopic data must be carefully analysed to ensure accurate descriptions and analyses are

employed.

In this presentation the use of spectroscopic and computational methods in the

characterisation of radical cations [{Cp*(dppe)Ru}{ -bridge}{Ru(dppe)Cp}]+ will be

described. Through variation in the nature of the bridging moiety it is possible construct

systems that behave as pseudo-classical mixed valence systems (illustrated below for a

diethynyl carboranyl bridged system), offer highly delocalised electronic structures or

bridging-ligand centred radical character.

0

250

500

750

1000

18003800580078009800 (cm-1)

-1cm-1) IVCT

IC

Observed

10/4/2008 KL2 11:10 – 10:55

Half-sandwich metallocarbonyl -N-imidato complexes in

bioorganometallic chemistry

Janusz Zakrzewski,

Department of Chemistry, University of Lodz, 90-136 Lodz, Narutowicza 68, Poland

[email protected]

The aim of the lecture is to present synthesis of CpM(CO)x ( -N-imidato) complexes ( M =

Fe, Mo, W; n = 2 or 3), their electronic structure and reactivity toward various biomolecules.

These complexes have been used as IR-detectable labeling reagents for proteins. To increase

the sensitivity of the detection, metallocarbonyl dendrimers have been synthesized and

coupled e.g. with anti-analyte antibodies. Some of the title complexes display enzyme-

inhibiting activity (e.g. toward GST, papain).

Results presented in the lecture have been obtained, in large part, in collaboration with the

Prof. Jaouen’s team (ENSCP, Paris).

INVITED LECTURES

7/4/2008 IL1 8:30 – 9:05

Metal complexes and organometallic compounds as precursors for

electronic and ceramic materials. Old ligands, new tricks.

Piotr Sobota

Faculty of Chemistry, Wroc aw University, 14, F. Joliot-Curie, 50-383 Wroc aw, Poland

For the last two decades, there has been a growing interest in the development of the

chemistry of mixed-metal bi- and polynuclear oxo, alkoxo and alkoxo-organometallic

complexes. Such interest derives from their fascinating structural chemistry, interesting

catalytic properties, and high potential for industrial applications. High applicability of such

compounds is an effect of a cooperation of two different metals in a single molecule which

gives rise to properties that are not a simple sum of the properties of the individual metals and

is often crucial for a system to achieve a desired activity. The classical example would be the

cooperation of titanium and aluminum in an olefin polymerization catalyst. Instead, well-

defined group 2 heterobimetallic alkoxo complexes are known as very efficient single-source

precursors (SSP) for the fabrication of highly pure oxide-ceramic materials. These are crucial

for today’s technology and are utilized for the production of superconductors, microelectronic

circuits, sensors, and ferroelectric materials. In our research group we have synthesized

several structurally interesting heterobimetallic alkoxo-organometallic complexes containing

main group and transition metals.1 The lecture will highlight the synthesis of a mixed-metal

alkoxo-organometallic complexes, an excellent single-source precursors for oxide materials.

___________________________

1. (a) Jerzykiewicz L. B.; Utko J.; John .; Duczmal M.; Sobota P. Inorg. Chem. 2007, 46, 9024. (b) Utko, J.; Ejfler, J.; Szafert, S.; John, .; Jerzykiewicz, L. B.; Sobota, P. Inorg.Chem. 2006, 45, 5302. (c) Jerzykiewicz, L. B.; Utko, J.; Sobota, P. Organometallics 2006, 25,4924. (d) Utko, J.; Przybylak, S.; Jerzykiewicz, L. B.; Szafert, S.; Sobota, P. Chem. Eur. J.2003, 9, 181. (e) Sobota, P. Coord. Chem. Rev. 2004, 248, 1047. (f) Utko, J.; Szafert, S.; Jerzykiewicz, L. B.; Sobota, P. Inorg. Chem. 2005, 44, 5194. (g) John, .; Utko, J.; Jerzykie-wicz, L. B.; Szafert, S.; K pi ski, L.; Sobota, P. Chem. Mater. 2008 – sent for publication.

7/4/2008 IL2 13:00 – 13:35

Hydroxycarbenes in Catalysis – Platina-β-diketones as Model Complexes

Dirk Steinborn, Michael Werner, Sebastian Schwieger Institut für Chemie – Anorganische Chemie, Martin-Luther-Universität Halle-Wittenberg

Kurt-Mothes-Straße 2, 06120 Halle, Germany Beginning with an overview on hydroxycar-bene–metal complexes as intermediates in homo-geneously catalyzed processes, the electronicallyunsaturated (16 ve) platina-β-diketones 1, hy-droxycarbene complexes that are stabilized by intramolecular O–H···O hydrogen bonds to neighbored acetyl ligands (Scheme 1), will be presented. Analogously, organic β-diketones 2 are considered as enols stabilized by intramolecular O–H···O hydrogen bonds to keto groups. The strengths of the hydrogen bonds in type 1 complexes have been calculated to be up to twice as strong as those in acetylacetone.

PtO

HO

R

R

PtO

HO

R

R

ClCl

1

HCO

HO

HCO

HO

HCO

HO

Due to the electronic unsaturation, the platina-β-diketones 1 were found to readily un-dergo oxidative addition reactions with a wide variety of mono- and bidentate N, O, S and P donors L2/L L yielding diacetylhydridoplatinum(IV) complexes 3 (Scheme 2). Depending on the type of ligand L2/L L and the reaction conditions, these complexes can react in a C–H or H–X reductive elimination reaction yielding acetyl platinum(II) complexes 4a and 4b, respectively. Finally, the usage of platina-β-diketones 1 as precatalysts in hydrosilylation of olefins and acetylenes will be discussed.

PtL

L COMe

Cl

− MeCHO

L L L

LPt

COMe

H

COMe

Cl

PtO

HO

Me

Me

PtO

HO

Me

Me

ClCl Pt

OH

OMe

MeL

L1/2

bridge cleavage/ligand substitution

oxidativeaddition

reductiveelimination

Cl

1a 3

4a

PtL

L COMe

COMe4b

− HCl

Scheme 2

It seems that the stabilization of platina-β-diketones by O–H···O bridges to acyl ligands is perfectly balanced: On the one hand, they are stable enough to be handled without difficulties but, on the other hand, they are reactive enough to undergo a manifold of interest-ing, unexpected and entirely new reactions. Thus, further insight is achieved into elementary steps where hydroxycarbenes are involved which is of interest both for organometallic chem-istry and for homogeneous catalysis. Selected References (a) D. Steinborn, Dalton Trans. 2005, 2664 – 2671. (b) M. Werner, T. Lis, C. Bruhn, R. Lindner, D. Steinborn, Organometallics 2006, 25, 5946 – 5954. (c) D. Steinborn, S. Schwieger, Chem. Eur. J. 2007, 13, 9669 – 9678.

[Pt]O

HO

[Pt]O

HO

2

Scheme 1

7/4/2008 IL3 16:30 – 17:05

Bioinspired oxidation reactions with highly preorganized

dicopper complexes

Franc Meyer

Institut für Anorganische Chemie, Georg-August-Universität Göttingen, Tammannstrasse 4,

D-37077 Göttingen, Germany

Numerous enzymes take advantage of the cooperative action of two proximate metal ions

within their active site, in particular for multielectron redox transformations (e.g., for the

activation of O2 at dicopper sites and subsequent oxygenation and oxidation chemistry).

These natural systems represent a guiding line for novel bioinspired catalysts.[1] We have

prepared a series of highly preorganized bimetallic complexes based on compartmental

pyrazolate ligands, in which molecular parameters such as the metal-metal separation can be

tuned by appropriate modifications of the ligand scaffold.[2] These systems allow to study

structure/activity correlations in cooperative two-center reactivity.[3] Selected examples of

copper-mediated oxidation reactions as well as insight into structural and electronic details of

O2-activation at the multicopper sites will be presented.

Cu CuN N

H2O or H2O2

substrate

O2

This work is supported by the DFG (International Research Training Group GRK 1422;

www.biometals.eu)

[1] J. I. van der Vlugt, F. Meyer, Top. Organomet. Chem. 2007, 22, 191-240.

[2] see for example: J. Ackermann, F. Meyer, H. Pritzkow, Inorg. Chim. Acta 2004, 357,

3703-3711.

[3] a) A. Prokofieva, A. I. Prikhod’ko, E. A. Enyedy, E. Farkas, W. Maringgele, S.

Demeshko, S. Dechert, F. Meyer, Inorg. Chem. 2007, 46, 4298-4307; b) A. Prokofieva, A. I.

Prikhod’ko, S. Dechert, F. Meyer, Chem Commun. 2008, DOI: 10.1039/b718162k.

8/4/2008 IL4 8:30 – 9:05

Inorganometallics and catalysis

Bogdan Marciniec

Department of Organometallic Chemistry, Faculty of Chemistry,

Adam Mickiewicz University, Grunwaldzka 6, 60-780 Poznań, Poland

Numerous reactions of organic compounds catalyzed by TM complexes developed in

the last half century occur via active intermediates involving metal-carbon bonds i.e.

organometallics. Per analogy, organic derivatives of a heteroatom such as silicon, boron,

germanium and other p-block elements (E) in the presence of TM complexes undergo

transformations via respective intermediates containing metal-heteroatom (TM−E) bond

called inorganometallics [1, 2]. In these transformations these complexes are actual catalysts

and E does not play role of ancillary ligands but undergoes transformation to get products

(E−C, E−E, E−E’, where E = Si, Ge, B, Sn..).

The aim of the lecture is to present exemplary reactions occurring in the presence of

TM (M=Ru, Rh, Ir, Pd) complexes containing or generating TM−H or TM−E bonds, such as

hydrometallations and bismetallations and particularly trans-metallations. The latter reactions

based on catalytic activation of sp2 and sp-carbon-hydrogen bonds as well as O−H bond of

alcohols and silanols with vinylmetalloids (CH2=CH−E) can be summarized as follows [3]:

+ E' H RnE +

E = Si, B, Ge; E' H = C H, C H , C OH , Si OH

ER'n [TM]E'

H, [TM] E

A notable peculiarity of these processes is that they open as a new universal route for

synthesis of well-defined molecular and macromolecular compounds with E−E’ functionality.

References: [1] Felhner, T.P., Inorganometallic Chemistry, Plenum Press, New York, 1992. [2] (a) Marciniec, B., Pietraszuk, C., Kownacki, I., Zaidlewicz M. in Comprehensive Organic Functional Group Transformations II, A.R.Katritzky&R.J.K.Taylor, eds, Elsevier, Amsterdam, Vol.1, pp.941-1024, 2005; (b) Marciniec, B., Pawluć, P., Pietraszuk, C. Inorganometallic Chemistry in Encyclopedia of Life Support Systems (EOLSS), ed.; Bertini, I., Eolss Publ. Co. Ltd (on line, 2007). [3] (a) Marciniec, B., Coord. Chem. Revs, 2005, 249, 2374.; (b) Marciniec, B., Acc. Chem. Res., 2007, 40, 943-952; (c) Marciniec, B., Ławicka, H., Majchrzak, M., Kubicki, M., Kownacki, I., Chem., Eur.J., 2006, 12, 244; (d) Marciniec, B., Dudziec, B., Kownacki, I., Angew. Chem., Int.Ed., 2006, 45, 8180-8184.

8/4/2008 IL5 8:30 – 9:05

Coordination Chemistry of Divalent Carbon(0) Compounds – Theoretical Results and

Experimental Challenge

Gernot Frenking

Fachbereich Chemie, Philipps-Universität, Hans-Meerwein-Strasse, D-35043 Marburg,

Germany

The topic of the lecture are theoretical studies of coordination compounds with divalent

carbon(0) ligands which have the general formula CL2 where L is a electron donor. The

chemical bond between the ligand L and carbon is a L C donor-acceptor bond which means

that the carbon atom in CL2 carries two electron lone pairs. This makes divalent carbon(0)

compounds exceptionally strong donors. Experimentally known examples for CL2 are

carbodiphosphoranes1 C(PR3)2 which have already been synthesized in 1963.2 A theoretically

predicted new class of divalent carbon(0) compounds are carbodicarbenes C(NHC)2 (1) where

NHC = N-heterocyclic carbene.3 The latter compounds are related to tetraaminoallenes 2 (R =

NX2).4 The calculations predict that divalent carbon(0) compounds serve as strong Lewis

bases which yield main-group and transition metal complexes that possess promising

chemical properties which should be investigated with experimental methods.

PR3C

R3P

RNC

RN

CRN C

NRC C C

R

R

R

R

CDP 1 2

1 R. Tonner, F. Öxler, B. Neumüller, W. Petz, G. Frenking, Angew. Chem. 2006, 118, 8206;

Angew. Chem. Int. Ed. 2006, 45, 8038. 2 F. Ramirez, N. B. Desai, B. Hansen, N. McKelvie, J. Am. Chem. Soc. 1961, 83, 3539. 3 R. Tonner, G. Frenking, Angew. Chem. 2007, 119, 8850; Angew. Chem. Int. Ed. 2007, 46,

8695.4 R. Tonner, G. Frenking, Chem. Eur. J., in press.

9/4/2008 IL6 13:00 – 13:35

The Design of Mixed-donor Ferrocene Ligands

for Enantionselective Allylic Alkylation

Petr Št pni ka

Charles University in Prague, Faculty of Science, Department of Inorganic Chemistry

Hlavova 2030, 128 40 Prague, Czech Republic; E-mail: [email protected]

Enantioselective allylic substitution [1] has become a widely accepted testing tool used for

assessing the catalytic performance of chiral ligands. It also represents a powerful synthetic

method that allows stereoselective construction of new C–C bonds in functionalised

molecules.

A number of chiral ferrocene donors have been studied in this reaction with varying

success [2]. This contribution will deal with the preparation of two classes of novel chiral

ferrocene donors combining different coordination sites – chiral phosphinoalkenes [3] and

chiral phosphinoamides [4], and their utilisation in palladium-catalysed allylic alkylation.

Particular attention will be paid to investigations aimed at understanding the mechanism of

chiral information transfer from the ligand to the formed product.

[1] (a) B. M. Trost, D. L. Van Vranken, Chem. Rev. 1996, 96 395. (b) B. M. Trost, M. L.

Crawley, Chem. Rev. 2003, 103, 2921. (c) B. M. Trost, J. Org. Chem. 2004, 69, 5813. (d) T.

Hayashi, “Asymmetric Allylic Substitution and Grignard Cross-Coupling” in Catalytic

Asymmetric Synthesis (Ed.: I. Ojima), chapter 7.1, p. 325-365, VCH, New York 1993.

[2] (a) T. Hayashi, “Asymmetric Catalysis with Chiral Ferrocenylphosphine Ligands” in

Ferrocenes: Homogeneous Catalysis, Organic Synthesis, Materials Science (Eds.: A. Togni

and T. Hayashi), chapter 2, p. 105-142, VCH, Weinheim, 1995. (b) A. Togni, “New Chiral

Ferrocenyl Ligands for Asymmetric Catalysis” in Metallocenes (Eds.: A. Togni and R. L.

Halterman), vol. 2, chapter 11, p. 685-721, Wiley-VCH, Weinheim, 1998. (c) R. G. Arrayás,

A. Adrio, J. C. Carretero, Angew. Chem. Int. Ed. 2006, 45, 7674.

[3] (a) P. Št pni ka, I. Císa ová, Inorg. Chem. 2006, 45, 8785. (b) P. Št pni ka, M. Lama , I.

Císa ová, J. Organomet. Chem. 2008, in print.

[4] (a) M. Lama , I. Císa ová, P.; Št pni ka, Eur. J. Inorg. Chem. 2007, 2274. (b) M. Lama ,

J. Tauchman, J; I. Císa ová, P. Št pni ka, Organometallics 2007, 26, 5042.

10/4/2008 IL7 8:00 – 8:35

Organoantimony and organobismuth pincer compounds

Libor Dostál*

Department of General and Inorganic Chemistry, Faculty of Chemical Technology,

University of Pardubice, nám. s. Legií, 532 10, Pardubice, Czech Republic,

*[email protected]

Y,C,Y chelating, well known as pincer, ligands represent an extremely useful platform for

coordination chemistry of both transition and main group elements. These ligands can be

quite easily tuned at specific positions of their skeletons and it has usually pronounced

influence on chemical behavior of synthesized complexes especially central metals.

Pincer type complexes of heavier pnictogens (Sb, Bi) have become targets of scientific

interest only recently. The latest results concerning this field of hypervalent antimony and

bismuth compounds containing O,C,O and N,C,N ligands will be shown and discussed.

N

N

M

OR

OR

M

M = Sb, Bi

SHORT LECTURES

7/4/2008 S1 9:05 -9:20

Structural Relationships

in Polynuclear Bismuth Oxo Clusters

Dirk Mansfeld, Tobias Rüffer,b Heinrich Lang,b Markus Schürmann,a,b Michael Mehring*

Technische Universität Chemnitz, Institut für Chemie, 09107 Chemnitz, Germany a) Technische Universität Dortmund, Anorganische Chenie II, 44221 Dortmund, Germany

b) X-ray crystallography

The selective synthesis of metal oxide based materials with defined particle size is of

current interest within application-orientated research projects. Special focus is given to the

synthesis of nanoparticles. An important step on the way to prepare materials based on nano-

particular metal oxides is the control of the nucleation process. Polynuclear metal oxo clusters

may serve as model compounds for a better understanding of this process. In contrast to

transition metal oxo clusters few examples of structuraly characterized, main group metal oxo

clusters of high nuclearity, are known.

In line with our research on bismuth oxo compounds several intermediates in the course of

hydrolysis of monomeric precursors, for example bismuth silanolates, were isolated and

structurally characterized. The metal oxo clusters [Bi9O7(OSiMe3)13], [Bi18O18[OSiMe3)18]

and [Bi22O26(OSiMe2tBu)14] are representatives among these compounds [1-4]. The

characterization of structuraly related compounds contributes to the fundamental

understanding of the formation process and the assembly principles of bismuth oxido

particles. Here we present structural relationships between several bismuth oxo clusters.

partial

hydrolysis

Fig. 1 The formation of [Bi18O18[OSiMe3)18] by partial hydrolysis of [Bi(OSiMe3)3]3.

[1] D. Mansfeld, M. Mehring, M. Schürmann, Angew. Chem. Int. Ed. 2005, 44, 245. [2] M. Mehring, D. Mansfeld, S. Paalasmaa, M. Schürmann, Chem. Eur. J. 2006, 12 ,1767. [3] M. Mehring, S. Paalasmaa, M. Schürmann, Eur. J. Inorg. Chem. 2005, 24, 4891.[4] M. Mehring, Coord. Chem. Rev. 2007, 251, 974.

7/42008 S2 9:20 – 9:35

Water-soluble Platinum Clusters: Syntheses and Catalytic Activity

Mareike Meyera, Wolfgang Kläui*,a

aHeinrich-Heine-Universität, Universitätsstr. 1, 40225 Düsseldorf, Germany

Metal clusters of only a few nanometers in diameter can be considered to fill the gap from

binuclear metal complexes to the metallic state. Therefore they are of major interest in

catalytic research.

We succeeded in synthesizing water soluble platinum clusters of 2 – 4 nm in size by

reduction of an aqueous solution of K2PtCl4 with hydrogen gas in the presence of the

stabilizing ligand 2-diphenylphosphanoethyldisodiumphosphonate [1]. Furthermore, we are

able to define dimensions and size distribution of the emerging clusters by varying the

conditions during synthesis.

Scheme 1: Synthesis of water-soluble platinum clusters

H2 / H2On K2PtCl4 + m P

P

O

O-

O-2 Na+

The obtained clusters are stable when exposed to air and can be stored in solution over

months without coagulation. All clusters are efficient catalysts in the hydrogenation of

olefins. The catalytic activity is size-dependent; decreasing the main diameter increases the

activity. Due to their excellent water-solubility our platinum clusters are most promising

catalysts especially in “Green Chemistry”.

[1] Glöckler, J.; Klützke, S.; Meyer-Zaika, W.; Reller, A.; Garcia-Garcia, F. J.;

Strehblow, H.-H.; Keller, P.; Rentschler, E.; Kläui, W., Angew. Chem. 2006, 7, 1183-1186.

7/4/2008 S3 9:35 – 9:50

Arene Iron And Arene Ruthenium Complexes And Their Use For MOCVD

Applications

Ilona Jipaa, Katia Michkovab, Nadejda Popovskab, and Ulrich Zenneck*a

a* Department für Chemie und Pharmazie, Universität Erlangen-Nürnberg, Egerlandstrasse 1, D-91058 Erlangen, Germany

b Lehrstuhl für Chemische Reaktionstechnik, Universität Erlangen-Nürnberg, Egerlandstrasse 3, D-91058 Erlangen, Germany

Ruthenium thin films are of significant interest as promising candidates for

microelectronic applications like microelectrodes or microelectric contacts and thin films or

nanoparticles of iron at oxidic surfaces are of specific interest as catalysts for carbon nanotube

(CNT) formation. We investigate [(arene)(diene)M] derivatives systematically with M = Ru

and Fe as MOCVD (Metal Organic Chemical Vapor Deposition) precursors, which combine a

good vapor pressure with thermal decomposition temperatures below 200 °C and a well

controllable follow-up chemistry of the released ligands after the MOCVD process.[1]

[(Benzene)(1,3-cyclohexadiene)Ru] was investigated as a designed MOCVD precursor

where the inherent structural and chemical features of the ligands help the formation of pure

ruthenium films.[2] Main focus was spent to evaluate such process parameters, which grant

the purity of the deposited ruthenium films without the help of a reactive gas component.

[(1,3-Butadiene)(toluene)Fe] and a fluidized bed reactor were identified as an ideal

combination for the MOCVD of Fe nanoparticles (Fe-NP) or Fe thin films on oxidic powders

of different kind.[3] Several Fe coated powders were used successfully as heterogeneous

metal catalysts for a diameter controlled CNT preparation.

Fe(0) MOCVD

120 - 200°C

Fe-NP or Fe thin film

C2H2

700°CCNT

[1] A. Schneider, N. Popovska, F. Holzmann, H. Gerhard, C. Topf, U. Zenneck, ChemicalVapor Deposition, 2005, 11(2), 99.

[2] A. Schneider, N. Popovska, I. Jipa, B. Atakan, M.A. Siddiqi, R. Siddiqi, U. ZenneckChem. Vap. Deposition, 2007, 13, 389.

[3] K. Michkova, A. Schneider, H. Gerhard, N. Popovska, I. Jipa, M. Hofmann, U. Zenneck, Appl. Catalysis A: General 2006, 315, 83.

7/4/2008 S4 10:10 – 10:25

Element Organic Frameworks with high Permanent Porosity

Marcus Rose,a Winfried Böhlmann,b Stefan Kaskel*,a

aDepartment of Inorganic Chemistry, Dresden University of Technology,

Mommsenstr. 6, 01062 Dresden, Germany bFaculty of Physics and Earth Science, University of Leipzig,

Linnéstr. 5,04103 Leipzig, Germany

Porous materials such as metal-organic frameworks (MOFs, [1]) have high potential for

applications in adsorption, separation, gas storage and heterogeneous catalysis. Their modular

concept was used to develop a new class of highly microporous materials (d < 2 nm) that

combine properties like high hydrophobicity, high stability against water and good thermal

stability. In the following, we report the integration of elements such as silicon and their use

as connectors. At the same time, organic linkers are used to tailor the pore size, resulting in

porous, highly hydrophobic and thermally stable element organic frameworks (EOFs) via an

organometallic route. The primary building block Tetrakis(4-bromophenyl)silane [2] was

lithiated fourfold by reaction with n-butyllithium under inert conditions. Subsequent reaction

with tetraethylorthosilicate (TEOS) at 263 K resulted in the formation of the porous network

poly(1,4-phenylene)silane (EOF-1). A biphenylene linker was used to obtain larger pores in

poly(4,4’-biphenylene)silane (EOF-2) on a one-step reaction. EOF-1 and EOF-2 are X-ray

amorphous. They show no decomposition in air, moisture or aqueous solutions and have good

thermal stability in air up to 673 K. Both compounds are highly porous with specific BET

surface areas of 780 m2g-1 (EOF-1) and 882 m2g-1 (EOF-2) as determined from the nitrogen

physisorption isotherms measured at 77 K. Water adsorption isotherms at 298 K show a high

hydrophobicity for both materials. Summarizing, we have presented a new approach for the

design of hydrophobic microporous frameworks with accessible pore systems using organo-

element chemistry. In our view, an extension of the concept in terms of elements used as

nodes and organic linkers as connectors will lead to valuable adsorbents and catalyst supports

with well defined porosity and functionality.

[1] Kitagawa, S.; Kitaura R.; Noro, S.-I. Angew. Chem. Int. Ed. 2004, 43, 2334-2375.

[2] Fournier, J.-H.; Wang, X.; Wuest, J. D. Can. J. Chem. 2003, 81, 376-380.

7/4/2008 S5 10:25 – 10:40

Design and Characterization of Novel Chiral Building Blocks for the Construction of Functional Porous Materials

T. Kaczorowski,a J. Lewi ski,a W. Bury,a M. Dranka,a W. liwi ski,a I. Justyniak,b

J. Lipkowskib

aDepartment of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw, Poland

bInstitute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224

Warsaw, Poland

In the last decade, there has been tremendous interest in designing and synthesis of

functional solids based on metal-organic coordination networks. One of the most difficult

challenges in materials chemistry is to master synthesis of crystal networks with desired

topology and properties by appropriate choice of organic ligand (or organometallic

metalloligand) and metal precursor. The employment of various multitopic, conformationally

rigid and flexible ligands with different binding modes and strengths is very fruitful in the

construction of well-defined solid-state structures with expected physical and chemical

properties.

This report is focused on the construction of achiral and homochiral coordination

polymers combining homoleptic zinc alkyls, R2Zn, as connectors and different bipyridine-

type compounds as linkers. Various combinations of these subunits lead to zig-zag chains (I),

helices (II) and fabrics (III) with or without porous architecture.[1] The successful

construction of porous homochiral architectures was achieved by the employment of

alkylaluminum derivatives of cinchonine as metalloligands. The selected porous materials

demonstrated highly desirable properties of enantioseparation of racemic organic compounds

and gas sorption.

I II III

[1] Lewi ski, J.; Dranka, M.; Bury, W.; liwi ski, W.; Justyniak, I.; Lipkowski, J. J. Am. Chem. Soc. 2007, 129, 3096.

7/4/2008 S6 10:40 – 10:55

From supramolecular structures to intelligent surfaces

Schirrmacher, C.,a Bruhn, C.,a Siemelung, U.a, Käfer, D.b, Witte, G. b

aUniversität Kassel, Heinrich-Plett-Str. 40 , 34132, Kassel, Germany bRuhr-Universität Bochum, Universitätsstr. 150 ,44780 , Bochum, Germany

Surfaces that can react on external stimuli in a reversible manner ( so called smart

surfaces) are of big research interest. For this purpose we developed a modular synthetic

concept, using the sponanious self assembley of functional adhesive molecules which form

self assembled monolayers on Au(111) and HOPG. The adsorbing molecules are designed in

a molular way. The binding unit contains disc like thioetherfunctionalized phthalocyanines

and porphyrines. [1] The metall centre serves as “docking station for rod like assembley groups

containing spacer and terminal functional units. By this concept the functional units are lateral

separated and are able to fullfill their function without any disturbance by neighbour

molecules. A similar strategy was allready sucessfully used for tripodal bining groups[2] .

Planed and allready established functions are redoxactivity, photoisomerisation, complexation

of catalytic active metalls and immobilisation of oncogenic proteins.

[1] D. Woehrle, M. Eskes, K. Shigehara A. Yamada, Synthesis, 1993, 194–196. K. Takahashi, M. Kawashima, Y. Tomita M: Itoh, Inorg. Chim. Acta, 1995, 232,69–73

[2] T. Weidner, A. Krämer, C. Bruhn M. Zharnikov A. Shaporenko U. Siemeling F. Träger, Dalton Trans., 2006, 2767.

7/4/2008 S7 10:55 – 11:10

Selfassembled monolayers based on thiol functionalized

transition metal complexes

Katrin Döring,a Michael Zharnikov,b Andrey Shaporenkob, Tobias Weidnerb, Rudolf Holze,c

and Heinrich Lang*, a

a Technische Universität Chemnitz, Fakultät für Naturwissenschaften, Institut für Chemie,

Lehrstuhl für Anorganische Chemie, Straße der Nationen 62, 09111 Chemnitz, Germany. b Universität Heidelberg, Institut für Angewandte Physikalische Chemie, Im Neuenheimer

Feld 253, 69120 Heidelberg, Germany. c Technische Universität Chemnitz, Fakultät für Naturwissenschaften, Institut für Chemie,

Professur für Physikalische Chemie / Elektrochemie, Straße der Nationen 62, 09111

Chemnitz, Germany.

Different synthesis methodologies to prepare thiols of type R´ C C C6H4 C6H4 SR and

LnM C C C6H4 C6H4 SR (e.g., type A molecule: LnM = ( 5-C5H5)( 5-C5H4)Fe, ( 5-

C5H5)( 5-C5H4)Ru; R = H, COMe) will be reported [1]. The chemisorption of these molecules

from solution onto gold surfaces gave Self-Assembled Monolayers (SAMs), which have been

characterized by photoelectron spectroscopy, impedance, NEXAFS (near edge X-ray

absorption fine structure spectroscopy), and SERS (surface enhanced raman spectroscopy) [2,

3].

MC C SR

A

(M = Fe, Ru)

[1] K. Rößler, T. Rüffer, B. Walfort, R. Packheiser, R. Holze, M. Zharnikov, H. Lang, J.

Organomet. Chem. 692 (2007) 1530.

[2] A. Shaporenko, K. Rössler, H. Lang, M. Zharnikov, J. Phys. Chem. B 110 (2006) 24621.

[3] T. Weidner, K. Rössler, P. Ecorchard, H. Lang, M. Grunze, M. Zharnikov, J. Electroanal.

Chem. (2008) in print.

7/4/2008 S8 11:10 – 10:25

Spectroscopic and thermal properties of lanthanides (III) complexes with

2,2’-biphenyldicarboxylic acid

Justyna Sienkiewicz*, Zofia Rz czy ska, Alina Kula

Department of General and Coordination Chemistry, Faculty of Chemistry, Maria Curie-

Sk odowska University, 20-031 Lublin, Poland

The complexes of Y(III) and lanthanides(III) from La to Lu with 2,2’-biphenyldicarboxylic acid

were obtained as hydrated precipitates with the metal:ligand ratio of 2:3 and the general formula of

Ln2(C12H8(COO-)2· n H2O, where n=3 for the first isostructural series from La to Er and n=6 for the

second series of Tm, Yb and Lu(III) complexes.

The complexes were characterized by FTIR and Raman spectroscopy. The characteristic of

carboxyl vibrations in the free diphenic acid are found at 1685 cm-1 as strong vibrations of the

protonated carboxylic group COOH and also strong bands at 1412 and 1578 cm-1 assigned to the

symmetric and asymmetric C-O stretching vibrations of the other deprotonated carboxylic group of

acid. During coordination of metal ions the bands of 1685 cm-1 disappear in the spectra of complexes

and symmetric and asymmetric bands of the COO- groups appear. In the spectra of Y and La to Er the

asymmetric vibration bands of COO- groups are present at 1532-1521 cm-1 and symmetric vibration

bands of COO- groups are at 1412-1402 cm-1. The (COO-) values for each complex of La-Er(III)

group are smaller than those of Tm-Lu complexes and suggest that carboxylic group in those

complexes posses different coordination modes. In a high energy region in the IR spectra there are the

bands in range 3700-3100 cm-1, which indicates absorption peaks due to O-H bonds of water

molecules. These bands are associated with hydrogen bonds formation and change their positions with

changing the hydrogen bond energy.

The curve of TG/DTG and DTA thermal analysis show that hydrated complexes of lanthanides

from La-Lu heated in air lose all water molecules in one step. Temperature of dehydration process for

trihydrated complexes is about 150oC, but for heksahydrated complexes is lower down 100oC. The

anhydrous compounds are stable up to about 350oC in air atmosphere and decompose on heating

directly to the oxides; Ln2O3, Tb4O10 and Pr6O11. The temperature of oxide formation is in the range of

600-750oC, excepting 400oC (for Ce complex).

The gas product analysis which is connected with decomposition process was carried out for

gadolinium(III) complex as the representative complex for all isostructural compounds of Y and La-Er

group complexes. These spectra confirm, that not deamination takes place.

7/4/2008 S9 13:35 – 13:50

Immobilized Ru complexes on mesoporous molecular sieves as catalysts for

olefin metathesis

David Bek,a Hynek Balcar,a Jan Sedlá ek,b Ji í ejkaa

aJ.Heyrovský Institute of Physical Chemistry AS CR, v.v.i, Dolejškova 3, 182 23 Prague 8,

Czech Republic b Department of Physical and Macromolecular Chemistry, Faculty of Science, Charles

University, Albertov 2030, CZ-128 40, Prague 2, Czech Republic

Mesoporous molecular sieves with unique properties such large surface area, large void

volume and narrow pore size distribution represent modern supports for designing advanced

catalysts including catalysts for olefin metathesis [1]. New heterogeneous catalyst for ring

opening metathesis polymerization (ROMP) has been prepared by immobilization of

[RuCl2(p-cymene)]2 on siliceous mesoporous molecular sieve SBA-15 (SBET = 915 m2/g,

V = 1.10 cm3/g, d = 6.3 nm). The catalyst of 1 % weight content of Ru, was prepared by

stirring of dried SBA-15 with [RuCl2(p-cymene)]2 in CH2Cl2 at room temperature for 5 hours.

Activity of the catalyst was tested in ROMP of 2-norbornene in toluene (1).

nn (1)

After catalyst activation with trimethylsilyldiazomethane before reaction, high molecular

weight polynorbornene of Mw = (2.8–7.4)×105 in the yields up to 77 % were obtained (1 h,

60°C). The structure of polymer was proved by IR spectroscopy. Leaching of the immobilized

catalyst was not observed. Catalyst can be easily separated from reaction mixture in contrast

to the corresponding homogeneous system [2] and, therefore, polymeric product without

catalyst residues can be obtained.

[1] H.Balcar, J. ejka, in Metathesis Chemistry: From Nanostructure Design to Synthesis of

Advanced Materials, Y.Imamoglu, V.Dragutan (eds.), Springer 2007, pp. 151-166.

[2] A. Demonceau, A. W. Stumpf, E. Saive, A. F. Noels, Macromolecules 30, 3127-3136,

(1997).

7/4/2008 S10 13:50 – 14:05

Perfluoroalkylation by Cross-metathesis of Alkenes

Barbara Eignerová,a,b Martin Kotora*,a,b

aDepartment of Organic and Nuclear Chemistry, Faculty of Science, Charles University,

Hlavova 2030, 12843 Prague 2, Czech Republic b Institute of Organic Chemistry and Biochemistry, Czech Academy of Sciences, Flemingovo

nám. 2, 16610 Prague 6, Czech Republic

A number of compounds with attached perfluoroalkylated chains exhibit interesting

biological properties. Therefore, it is of general synthetic interest to develop new

methodology that would enable to introduce perfluoroalkyl groups into various molecules

under mild reaction conditions. Recently, it was shown that one such option is ruthenium

catalysed cross-metathesis with perfluoroalkylated ethenes [1].

Currently, we are working on a related methodology that would allow the synthesis of

arenes, ferrocenes, saccharides and steroids, bearing perfluoroalkyl substituents. Our

procedure is based on the cross-metathesis of easily available 3-perfluoroalkylpropenes with

compounds having the terminal double bond. Effect of the substrate structure on cross-

metathesis selectivity and reactivity and other mechanistic features will be presented.

R2 R2Ru-cat

RO

R2 =

R1 = C6F13, C3F7, i-C3F7

R1 R1

FeOAcO

AcOOAc

OAc

n

empty line (12 pt TNR)

[1] S. Imhof, S. Randl, S. Blechert Chem. Commun, 2001, 1692-1693.

7/4/2008 S11 14:05 – 14:20

Non-hydrolytic route to synthesis methylalumoxanes in reaction of aliphatic

dicarboxylic acids with trimethylaluminium, activity and applications.

M. Marczewski, a A. Boczkowska,b M. Siekierski,a A. Pietrzykowski*,a

Warsaw University of Technology, aFaculty of Chemistry, Noakowskiego 3, 00-664 Warsaw; bFaculty of Materials Science and Engineering, Woloska 141, 02-507 Warsaw, Poland

Methylalumoxanes (MAO) are one of the most studied classes of organoaluminium

compounds. This is due to their important role in catalytic systems used in olefin

polymerization.

Here we report the non-hydrolytic method of synthesis of methylalumoxane. The reactions

between aliphatic dicarboxylic acids (malonic, adipinic, succinic, itaconic) and

trimethylaluminium at various molar ratios were studied. According to a method developed in

our group new methylalumoxanes containing eight aluminium atoms per molecule have been

recently synthesized [1]. The activity of synthesized compounds was tested towards styrene

polymerization and compared to activity of commercially available methylalumoxane.

Methylalumoxanes obtained from itaconic and succinic acids have been used as

components improving properties of polyurethanes and in synthesis of polymer electrolytes.

The mechanical properties of prepared polyurethanes and properties of polymer electrolytes

will be discussed on the presentation.

[1] A. Pietrzykowski, T. Skrok, S. Pasynkiewicz, T. Radzymi ski, K. Suwi ska, unpublished

data

7/4/2008 S12 14:40 – 14:50

Catalyst development for hydroformylation of long-chain olefins in sc CO2

Cezar Ionescu, Olaf Walter, Stephan Pitter, Eckhard Dinjus

ITC-CPV, Forschungszentrum Karlsruhe, D-76201 Karlsruhe, Germany.

The hydroformylation is one of the most important industrial applications of

homogeneous catalysis including for short chains olefins an effective catalyst recycling as

shown in the Rhone-Poulenc-Ruhr-Chemie process. For long chain olefins however still some

development for an effective catalyst recycling is needed.

One possibility offers the application of sc CO2 (low Tc and pc) as the solvent in

catalysis. Two different approaches for catalyst recycling are presented here (Scheme 1):

A) The application of the sc CO2 as solvent under homogeneous reaction conditions

with following separation of the catalyst by simple changing of p, T [1, 2].

B) The application of sc CO2 as solvent and mobile in supported ionic liquid phase

(SILP) and supported catalysis.

Scheme 1. Possible separation approach

The results of these different approaches will be presented including the physical

chemical background for the phase separation technology (A) as well as an evaluation of their

feasibility.

[1] Patcas F., Maniut C., Ionescu C., Pitter S., Dinjus E. Appl. Cat. B. 2007, 70, 630-636.

[2] Pitter S. in Topics in Organometallic Chemistry, Brown J. M. (Ed.), Chemie und

Materialwissenschaften, Springer-Verlag, Berlin/Heidelberg, 2006, S. 3418-3441.

7/4/2008 S13 14:55 – 15:10

Catalytic activity of Pd(II) complexes with triphenylphosphito ligands in

Sonogashira reaction in ionic liquids media

Izabela B aszczyk, Anna M. Trzeciak, Józef J. Zió kowski

Faculty of Chemistry, University of Wroc aw, 14 F. Joliot-Curie, 50-383 Wroc aw, Poland

Orthopalladation reaction is an activation of the ortho-C-H bond in phenyl ring leading to the

formation of new Pd-C bond. Complexes of that type have reactive C-Pd bond and are

additionaly stabilized by coordination of the triarylphosphite ligands (Pd-P bond) to

palladium, what can present interesting reactivity in C-C bond forming processes. As a result

of the organometallation reaction two new palladacycle complexes with substituted

triarylphosphito ligands P(OR)3 (R = m-MeC6H4, o-MeC6H4) have been prepared. The

reactivity of the obtained complexes as well as their non-orthometallated analogues,

PdCl2[P(OR)3]2, has been tested in copper-free Sonogashira reaction.

I H[Pd]

NEt3, IL+

Reaction conditions: [Pd] 1 mol%; [PhI] 1 mmol; [PhC CH] 1 mmol; [NEt3] 1.9 mmol; [IL] 1.5 ml; 80oC; t= 1 or 4 h

All reactions were carried out using iodobenzene and phenylacetylene as a substrates, NEt3

as a base and reducing agent and imidazolium ionic liquids as solvents. The [bmim][PF6] and

[emim][SO4C2H5] ionic liquids has been chosen. The application of ionic liquids as reaction

media instead of organic solvents makes it possible to construct recyclable catalytic system

what also has been tested. The obtained palladium complexes show high activity in both ionic

liquids. The yield of diphenylacetylene depends on the kind of catalyst precursor and ranged

from 31 to 98%. The best results were obtained for PdCl2[P(O-m-MeC6H4)3]2 (84%) and for

orthopalladated dimer with the same phosphite (98%) in [bmim][PF6].

R. B. Bedford, S.L. Hazelwood, M.E. Limmert, D.A. Albisson, S.M. Draper, P.N. Scully, S.J. Coles, M.B. Hursthouse, Chem. Eur. J., 9

(2003), 3216-3227

7/4/2008 S14 15:10 – 15:25

Allenylidene Complexes of Palladium.

Synthesis and Catalytic Properties

Florian Kessler, Helmut Fischer*

University of Konstanz, Universitätsstraße 10 , 78457, Konstanz, Germany

Chromium complexes containing a -donor substituted allenylidene ligand are readily

available in an easy to perform one-pot fashion. Reaction of (CO)5Cr[THF] with appropriate

deprotonated alkynes as the cumulenylidene precursor, followed by alkylation of the resulting

alkynylchromate with R3O[BF4] yields the corresponding allenylidene complexes in high

yields. The allenylidene ligands may be transferred from chromium to tungsten [1].

However, a transfer of the allenylidene ligands to catalytically active late transition metals

like palladium could not be realized. We now report on a direct straightforward route to

palladium allenylidene complexes starting from commercially available N,N-

dimethylpropiolamide as the C3-source, e.g.

H C C CO

NMe2

1.) NBS, AgNO32.) Pd(PPh3)4

3.) MeOTfBr Pd C C C

PR3

PR3

OMe

NMe2

OTf

The new palladium allenylidene complexes are active pre-catalysts in Mizoroki-Heck C-

C-coupling reactions. The dependence of the activity of the allenylidene complexes on the co-

ligands will be discussed.

[1] Szesni, N.; Drexler, M.; Fischer, H. Organometallics 2006, 25, 3989.

7/4/2008 S15 15:25 – 15:40

New 1 -(Diphenylphosphanyl)ferrocencarboxamides Bearing

2-Hydroxyethyl Groups at the Amide Nitrogen

Ji í Schulz, Ivana Císa ová, Petr Št pni ka*

Department of Inorganic Chemistry, Faculty of Science, Charles University, Hlavova 2030,

12840 Prague, Czech Republic; E-mail: [email protected]

While studying the coordination and catalytic chemistry of ferrocene phosphinocarboxylic

ligands [1], we turned also to the corresponding phosphinoamide derivatives [2]. As a

contiuation of our work, we decided to prepare two new phosphinoferrocenyl amides bearing

2-hydroxyethyl chains at the amide nitrogen and to study their coordination and catalytic

properties.

Carboxamides 1 and 2 have been synthesized by amidation of 1´-(diphenylphosphino)-

ferrocenecarboxylic acid (Hdpf) [1,3]. Due to polar nature of 1 and 2 and the possibility of

forming hydrogen bonds, these ligands may exert good solubilities in polar reaction media

and also serve as usefull synthons for supramolecular coordination chemistry. Hence,

palladium complexes [PdCl2L2] (3, L = 1; 4, L = 2) were also syntesized. As revealed by X-

Ray diffraction studies, the ligands and their complexes associate in the solid state by means

of hydrogen bonds, forming supramolecular arrays the complexity of which ranges from one-

dimensional chains to complicated three-dimensional networks. The palladium komplexes 3

and 4 were succesfully tested in Pd-catalyzed Suzuki reaction in polar solvents.

1 2

Fe

PPh2

C

NH

O

OH

Fe

PPh2

C

N

O

OH

OH

[1] P. Št pni ka, Eur. J. Inorg. Chem., 2005, 19, 3787.[2] M. Lama , J. Tauchman, I. Císa ová, P. Št pni ka, Organometallics, 2007, 26, 5042; J. Kuehnert, M. Dušek, J. Demel, H. Lang, P. Št pni ka, Dalton Trans., 2007, 26, 2802; P. Št pni ka, J. Schulz, I. Císa ová, K. Fejfarová, Collect. Czech. Chem. Commun, 2007, 72,453; M. Lama , I. Císa ová, P. Št pni ka, Eur. J. Inorg. Chem., 2007, 16, 2274.[3] J. Podlaha, P. Št pni ka, J. Ludvík, I. Císa ová, Organometallics, 1996, 15, 543.

7/4/2008 S16 15:40 - 15:55

Palladium complexes with NHC ligands used as catalysts of Suzuki –

Miyaura reaction in green solvents.

M. S. Szulmanowicz A. M. Trzeciak

Faculty of Chemistry, University of Wroclaw, 14 F.Joliot-Curie, 50-383 Wroclaw, Poland

Suzuki - Miyaura reaction is a very important way of biaryl compounds synthesis used as

non-steroidal anti-inflammatory drugs, anti-pain drugs and pesticides. Palladium complexes

with N – heterocyclic carbene (NHC) ligands have found many

applications in C-C cross-coupling reactions. Three new carbene

complexes of palladium Pd(moktim-y)2Cl2, Pd(miop-y)2Cl2 and

Pd(bmim-y)2Br2 were obtained and used as catalyst precursors

in the model Suzuki- Miyaura reaction of 2–bromotoluene and

phenylboronic acid. The reaction product, 2-methylbiphenyl,

may be used in the food industry.

N

N

Pd N

N

X

X

CH3

H3C

R

R

R= -C4H9, -C8H17, CH2OC3H7X= Cl, Br

Fig. 1 [Pd]=

CH3 B(OH)2

[Pd]NaHCO3

BrCH3

2 - methylbiphenyl2 - bromotoluene phenylboronic acid

1100C

Fig. 2

The aim of our research was to check the activity of palladium complexes in the Suzuki

reaction in ecological solvent like water or ethylene glycol. We found that carbene complexes

Pd(bmim-y)2Br2, Pd(moktim-y)2Cl2, Pd(miop-y)2Cl2 are good catalyst precursors of the

Suzuki- Miyaura reaction. We received 50% yield of product in water and 90% - 97% yield in

ethylene glycol. During the reaction Pd(0) nanoparticles were formed in situ and isolated from

the reaction mixture after immobilization on Al2O3. It was found that Pd(0) is catalytically

active and the reaction yield depends on the size of nanoparticles.

C. J. Mathews, P. J. Smith, T. Welton, J. Mol. Catal A: Chemical 206 (2003) 77-82

L. Xu, W. Chen, J.Xiao, Organomet., 19 (2000) 1123-1127

7/4/2008 S17 15:55 – 16:10

Phosphinoferrocene Amides Derived from Glycine – Synthesis,

Coordination Properties, and Catalytic Utilization

Ji í Tauchman, Ivana Císa ová, Petr Št pni ka*

Charles University in Prague, Faculty of Science, Department of Inorganic Chemistry,

Hlavova 2030, 128 40, Prague, Czech Republic; E-mail: [email protected]

For quite a long time, our group has focused on the chemistry of ferrocene-based

phosphanylcarboxylic acids and their derivatives [1]. In recent years we have studied mainly

phosphinoferrocene amides that combine central and planar chirality (e.g., 1 3) [2,3]. Donors

of this type are not only versatile ligands but also proved to be useful catalyst components for

both enantioselective and achiral metal-mediated organic transformations.

With this contribution, we report on the preparation of the first ‘conjugates’ of a carboxy-

phosphinoferrocene unit with an amino acid, viz. compounds 4. Coordination ability of these

new ligands has been probed in Pd(II) complexes and their catalytic properties were tested in

Suzuki-Miyaura cross-coupling reaction.

Fe C(O)NH

PPh2

Me

Ph

R

Fe

R

PhC(O)NH

PPh2

Fe

C(O)NHCH2CO2R

PPh2

1R = H (Rp,R)R = Me (Rp,R,R), (Rp,R,S)

Fe

PPh2

C(O)NHPh

R

2R = H (Sp)R = Me (Sp,R), (Sp,S)

3R = Me (R), (S)

4R = H, Me

[1] Št pni ka, P. Eur. J. Inorg. Chem. 2005, 3787.

[2] Lama , M; Císa ová, I.; Št pni ka, P. Eur. J. Inorg. Chem. 2007, 2274.

[3] Lama , M.; Tauchman, J.; Císa ová, I.; Št pni ka, P. Organometallics. 2007, 26, 5042.

7/4/2008 S18 17:05 – 17:20

A biopolymer as stabilizing agent of gold nanoparticles

Irene Domínguez, Avelino Corma, Patricia Concepción, Vicente Fornés and

María J. Sabater*

Instituto de Tecnología Química UPV-CSIC, Universidad Politécnica de Valencia,

Avenida de los Naranjos s/n, 46022 Valencia, Spain

Gold nanoparticles are already being used in a range of applications [1] and it is

particularly exciting its use in catalysis.

During 1980s, Haruta [2] found that small gold particles supported on different oxides can be

used to oxidize CO at less than 0 °C. From then on, the synthesis of gold nanoparticles has

received a lot of attention, different supports, stabilizing and reducing agents have been used

for this purpose [3].

We have carried out the formation of gold nanoparticles using a biopolymer, chitosan, as

stabilizer of gold nanoparticles with not additional reducer. The chitosan was deposited on

silica in order to improve the weak mechanical properties and poor diffusion of the

biopolymer. Two materials with different chitosan/SiO2 ratio were synthesized. Before and

after gold incorporation the solids were characterized by different techniques what led us to

study the metal-support interactions. This interaction, between gold and NH and OH groups

of chitosan, could allow good dispersion of nanocrystals on the biopolymer what could

contribute to the benefits found in chitosan with respect to others supports [4].

Determination of metal particle sizes by TEM showed an average particle size of 4-6 nm and

2-4 nm for the material with lower and higher chitosan/SiO2 ratio respectively, what showed

the important stabilizer power of this biopolymer.

[1] Thompson, D. T. Nanotoday. 2007, 2, 40-43

[2] Haruta, M.; Yamada, N.; Kobayashi, T.; Iijima, S. J. Catal. 1989, 115, 301-309

[3] Haruta, M. Gold Bull. 2004, 37, 1-2, 27-36

[4] Corma, A.; Concepción, P.; Domínguez, I.; Fornés, V.; Sabater, M. J. J. Catal. 2007, 251,

39-47

7/4/2008 S19 17:20 – 17:35

New Polymer-Metallodrug Conjugates for Cancer Diagnostics

Nadine E. Brückmann,a Peter C. Kunz,*,a

aHeinrich-Heine-Universtiy of Düsseldorf, Universitätsstr. 1, 40225, Düsseldorf, Germany

In order to improve current cancer pharmaceuticals, new transport systems are developed

that deliver drugs directly to tumors, where the drug can subsequently be released. This

delivery is made possible by the fact that macromolecules accumulate in tumors due to the

EPR-Effect [1]. Although polymers are now widely used in therapeutic approaches, only a

few examples of diagnostically used polymer-conjugates exist [2]. The use of technetium as a

radiotracer is of particular interest to cancer diagnostics and its chemistry is best resembled by

its heavier congener rhenium. Therefore, macromolecules carrying ligands that are able to

bind M(CO)3 (M = Tc, Re) are interesting for diagnostic as well as therapeutic (in the case of 188Re) approaches.

O NH

OH

n m

N

N

ReN

CO

OC CO

We developed the polymerizable ligand bis(2-pyridylmethyl)-4-vinylbenzylamine (L), a

chelating ligand suitable for the coordination of M(CO)3-fragments. Copolymerization of the

ligand with N-(2-hydroxypropyl)methacrylamide (HPMA) results in a biocompatible

copolymer-backbone capable of carrying the medically interesting technetium and rhenium

cores directly into the tumor tissue.

[1] Maeda, H.; Wu, J., Sawa, T., Matsumura, Y., Hori, K. J. Cont. Rel. 2000, 65, 271-284.

[2] Mitra, A.; Nan, A., Ghandehari, H. et al. Pharm. Res. 2004, 21:7, 1153-1159.

[3] Alberto, R., Ortner, K., Whealey et al. J. Am. Chem. Soc. 2001, 123, 3135.

[4] Kunz, P. C.; Brückmann, N., Spingler, B. Eur. J. Inorg. Chem. 2007, 3, 394-399

7/4/2008 S20 17:35 – 17:50

Synthesis of ferrocenyl conjugates of thioanalogs of steroids and nucleosides via the Mitsunobu reaction using

N-(ethoxycarbonyl)ferrocenecarbothioamide as the pronucleophile

Anna Wrona, Janusz Zakrzewski*

Department of Organic Chemistry, University of Lodz, Narutowicza 68, 90-136 Lodz, Poland

The introduction of redox-active ferrocenyl groups into biomolecules is one of the hot

topics in bioorganometallic chemistry [1]. In this communication we report on the use of N-

(ethoxycarbonyl)ferrocenecarbothioamide 1 [2] in synthesis of ferrocenyl conjugates of the

thioanalogs of some hydroxyl-containing biomolecules. We have found that 1 undergoes the

Mitsunobu reaction with alcohols and PPh3/DEAD to afford thioimidates 2.

FeS

NCOOEt

H

FeS

N COOEt

R

1 2

Using this reaction we have synthesized e.g. ferrocenyl conjugates of thiocholesterol 3,

protected 5’-thioadenosine 4 and 2’-deoxy-5’-thioadenosine 5.

FeN

S

COOEt

N

NN

N

NH2

O

OH

FeN

S

COOEtN

NN

N

NH2

O

OO

Fe

N

S

EtOOC

3

4 5

[1] Van Staveren, D. R.; Metzler-Nolte, N. Chem. Rev, 2004, 104, 5931-5985

[2] Pla uk, D.; Zakrzewski, J.; Rybarczyk-Pirek, A.; Domaga a, S. J. Organomet. Chem.

2005, 690, 4302-4308

7/4/2008 S21 17:50 – 18:05

Imidazolylphosphanes for Medicinal Bioorganometallic Chemistry

Wilhelm Huber,a Peter C. Kunz,*,a

aHeinrich-Heine-Universtiy of Düsseldorf, Universitätsstr. 1, 40225, Düsseldorf, Germany

Tris(imidazolyl)phosphines (TIP) show versatile coordination chemistry. We developed

the novel imidazol-4(5)-ylphosphane class of ligands (4-TIP) besides the long known

imidazol-2-yl-phosphanes (2-TIP) [1]. The 4-TIP ligands are more stable to hydrolysis and

show different hydrophilicity/hydrophobicity (e.g. water solubility) depending on the

substitution pattern of these compounds.

N

N

N

N

P N

N

R2 R2 R2

R1R1

R1

NNH

R

NHN

R

P

NNH

R

RuNN

ClP

O

N

NH

NN

P

NMOC

OCCO

2-TIP 4-TIP I II

Here we present several complexes of these ligands related to medicinal bioorganometallic

chemistry. With 4-tris(2-isopropyl-imidazolyl)phosphine oxide (4-TIPOiPr) the complex I was

synthesized. Half-sandwich Ruthenium(II) complexes of the type [Ru( 6-arene)(L)Cl]+ are

known as anti-tumor agents and even show cytotoxicity in cis-platin resistant cells lines.

Analogues to cis-platin they bind to DNA oligonucleotides forming monofunctional adducts.

[4]. Inert binding of TIP to the M(CO)3+ fragment (M = Mn, Tc, Re) leads to interesting

moieties (II) for diagnosis (99mTc, t½ = 6 h, E = 140 keV) and therapy (188Re, t½ = 19,6 h, E

= 2,1 MeV, 186Re, t½ = 88,9 h, E = 1,09 MeV; Mn(CO)3 as CORM). Especially the use of

metal complexes as CO-releasing molecules (CORM) is a rising field [3].

[1] Kunz P. C., Reiß G. J., Frank W., Kläui W., Eur. J. Inorg. Chem. 2003, 3945-3951; Kunz

P. C., Kläui W., Collect. Czech. Chem. Commun. 2007, 72, 492-502.

[2] Alberto R., J. Nucl. Radiochem. Sci., 2005, 6, 173-176.

[3] Alberto R., Motterlini R., Dalton Trans., 2007, 1651-1660.

[4] Chen H., Parkinson J. A., Morris R. E., Sadler P. J., J. Am. Chem. Soc. 2003, 125, 173-

186.

8/4/2008 S22 9:05 – 9:20

Ferrocene Diphosphanes with Planar Chirality –

Ligands for Enantioselective Catalysis

Martin Lama , Ivana Císa ová, Petr Št pni ka*

Charles University in Prague, Faculty of Science, Department of Inorganic Chemistry

Hlavova 2030, 128 40 Prague, Czech Republic; E-mail: [email protected]

We have recently reported utilisation of several (phosphanyl)ferrocenecarboxylic acids,

and related amides combining planar and central chirality as ligands in enantioselective

palladium-catalysed allylic alkylation reaction [1,2]. As a next step in investigating the role of

individual chirality elements and the different donor atoms available in the ligands, we have

turned to compounds derived from well known 1,1'-bis(diphenylphosphanyl)ferrocene, dppf

[3]. Thus, acid 1 has been prepared in a racemic form from 1,1'-dibromoferrocene, and

subsequently resolved into the enantiomers via the corresponding ester 2 with a chiral sugar

derivative – diacetone-D-glucose. Our current research is aimed at exploiting the coordination

behaviour of both racemic and optically pure ligands and, particularly, at catalytic testing of

chiral compounds in enantioselective allylic alkylation.

PPh2

COOH

PPh2

Fe

1PPh2

Fe

2

PPh2

O

OO

OO

O O

[1] Lama , M; Císa ová, I.; Št pni ka, P. Eur. J. Inorg. Chem. 2007, 2274.

[2] Lama , M; Tauchman, J; Císa ová, I.; Št pni ka, P. Organometallics 2007, 26, 5042.

[3] For an extensive review of the chemistry of dppf ligand, see: Gan, K.-S.; Hor, T.S.A. in

Ferrocenes: Homogeneous Catalysis, Organic Synthesis, Materials Science; Togni, A.;

Hayashi, T. Eds.; VCH: Weinheim, 1995; Chapter 1, pp. 3–104.

8/4/2008 S23 9:20 – 9:35

VANADIUM COMPLEXES OF THE ONNO - TYPE LIGAND.

SYNTHESIS, CHARACTERIZATION AND REACTIVITY

Tomasz Nerkowski, Zofia Janas and Piotr Sobota

Faculty of Chemistry, University of Wroc aw, 14 F. Joliot - Curie

50-383 Wroc aw, Poland

It is well known that vanadium complexes occurs in many biological systems in which its

coordination environment is created by O, S, N donor ligands.[1] The studies of sulphur-rich

ligation of vanadium has been an increased interest due to the effort of understanding of

vanadium nitrogenase, enzyme that catalyses the reduction of dinitrogen to ammonia and

converting of acetylene into ethene and ethane. In these both aspects vanadium complexes

containing 2,2’-oxydiehanethiolate (SOS)2- and 2,2’-thiobis{4-(1,1,3,3-tetramethyl-

buthyl)phenolate} (OSO)2- ligands have been studied in our laboratory. It was shown that the

vanadium centre ligated with the (SOS)2 ligand are adept at binding coligands such as hydrazine,

hydrazido(2-), nitrido, relevant to the nitrogenase.[2] Furthermore, this ligand as well as (OSO)2-

ligand create highly active single-site vanadium catalysts for ethene polymerization.[3] As a part

of our ongoing study on these both aspects we were interested in preparation, structural study and

reactivity of new vanadium complexes with the N,N-dimethylethylenediamino-bis(2-methylene-

1,1,3,3-tetramethyl-buthylphenolate) (ONNO)2- ligand (Scheme).

N

HO

HO

=HO

NN

HO

1. +4n-BuLi; -4n-BuH ( hexane)2. 2[VCl3(THF)3]; -4LiCl

V V

O

O

N

N

N

N

O

OCl

Cl

N 22

[1] Crans D. C.; Smee J. J.;Gaidamauskas E.;Yang L., Chem. Rev. 2004, 104, 849.

[2] Janas Z.;Sobota P., Coord. Chem. Rev., 2005, 249, 2144;

[3] Janas Z.; Jerzykiewicz L.B.; Richards R.L. and Sobota P., Chem. Commun., 1999, 1105; Janas Z.; Jerzykiewicz

L.B.; Przybylak S.; Richards R.L. and Sobota P., Organometallics, 2000, 19, 4252; Janas Z.; Wi niewska D.;

Jerzykiewicz L.B.; Sobota P.; Drabant K.; Szczegot K., Dalton Trans., 2007, 2065.

8/4/2008 S24 9:35 – 9:50

Metal Complexes with Aryloxo, Aminobisaryloxo

and Aryloxoimine Ligands - Synthesis and Catalytic Activity

Katarzyna Krauzy - Dziedzic, S awomir Szafert, Jolanta Ejfler, Piotr Sobota*


Transition and main group metal aryloxides is a fast growing family of complexes that

find application in numerous areas of chemical industry. The very early interest in such

compounds as lubricants is now driven out by their use in synthetic organic chemistry -

especially in enantioselective synthesis and catalysis [1]. They also find increasing application

as initiators and catalysts in different polymerization processes [2].

Simple homoleptic metal aryloxides, although well known, are not very common. We

have lately prepared an interesting titanium 7-benzofuranoxide by direct reaction of Ti(OiPr)4

or TiCl4 with commercially available 2,3-dihydro-2,2-dimethyl-7-benzofuranol (1). This

simple, monomeric in solution complex has proven to be an excellent initiator for ROP of

cyclic esters and good catalyst in the addition of terminal acetylenes to aryl aldehydes [3].

Based on this result we have prepared a series of Ti, Zr and Mg complexes with different

aminobisaryloxo (2) and aryloxoimine (3) ligands that were obtained in Mannich type

reaction from 3,5-disubsituted phenols, formaldehyde and primary amines.

The complex preparation and initial results of their catalytic activities will be presented.

O CH3

CH3

OH

tBu

tBuOH

N

tBu

tBuOH

O tBu

tBuOH

NR CH3

H3C

HO

CH3

CH3

R =

1 2 3

* * *

*

[1] (a) Gao, G.; Moore, D.; Xie, R. G.; Pu, L. Org. Lett. 2002, 4, 4143. (b) Xu, M. H.; Pu, L.

Org. Lett. 2002, 4, 4555.

[2] (a) Williams, C. K.; Breyfogle, L. E.; Choi, S. K.; Nam, W.; Young, V. G.; Hillmayer, M.

A.; Tolman, W. B. J. Am. Chem. Soc. 2003, 125, 11350.

[3] Krauzy-Dziedzic, K.; Ejfler, J.; Szafert, S.; Sobota, P. Dalton Trans. in press.

8/4/2008 S25 10:10 – 10:25

Heteromultimetallic Transition Metal Complexes

C. Schreiner, R. Packheiser, B. Walfort and H. Lang*

Technische Universität Chemnitz, Fakultät für Naturwissenschaften, Institut für Chemie,

Lehrstuhl für Anorganische Chemie, Straße der Nationen 62, 09111 Chemnitz, Germany.

E-mail: [email protected]

The study of heteromultinuclear transition metal complexes in which different metal

atoms are connected by -conjugated organic and/or inorganic carbon-rich bridging units is an

intriguing area of research, since such species may offer the possibility to study electronic

communication between the redox-active termini, exhibit non-linear optical properties or

provide, for example, cooperative effects in homogeneous catalysis.[1]

We report on the synthesis of novel heteromultimetallic complexes of structural type A – C.

Fe

N N

CC

CC

CC

Re

CO

OC

OC

tBu tBu

Ru

PPh3Ph3P

FeP

Ph2C C

N N

C CCC

Me3Si SiMe3

[Ti]

M

X+ -Au

M = Cu, X = PF6M = Ag, X = ClO4

A B

C CN N

C CCC

Me3Si SiMe3

[Ti]

Cu

PF6Ru

Fe

PPPh2

Ph2 C C PPh2

Au+

-

C

The structural and electrochemical properties of the resulted heterotri- to hetero-pentametallic

complexes is discussed.

1) Heinrich Lang, Rico Packheiser and Bernhard Walfort Organometallics 2006, 25, 1836.

8/4/2008 S26 10:25 – 10:40

Unexpected Titanocene Cyclopentadienide/Alkoxo Group Exchange

Anna Dr g, Józef Utko, ukasz John, Lucjan B. Jerzykiewicz, and Piotr Sobota*


The chemistry of metal sandwich group 4 metallocenes has attracted considerable

attention due to their applications in stoichiometric and catalytic reactions [1]. This rich

chemistry is dominated by their applications in olefin polymerization and is also promoted by

noteworthy transformations, involving reduction to Cp2Ti(III) and Cp2Ti(II) species, loss of

ring to give TiCl3Cp compound, and replacement of halogen by other unidate ligands.

As a part of our ongoing study we were interested in the preparation of mixed-metal alkoxo-

organometallic single-source precursors (SSP) for highly pure oxide-ceramics possess

perovskite structure. This has prompted us to study the behavior of titanocene TiCl2Cp2

towards exchange chlorine atoms with metal alkoxo species. The successful route to

substitution of titanium ligands in TiCl2Cp2 by 2-methoxyethanol is shown in Scheme. Direct

reaction of TiCl2Cp2 with metallic Sr, Ca and Mn in 2-methoxyethanol gave unexpected

cyclopentadienyl-free colorless heterometallic 1-3 complex.

TiCl

Cl

[Sr4Ti2( µ4-O)Cl4(OCH2CH2OCH3)10(HOCH2CH2OCH3)2] [Ca4Ti2( µ6-O)Cl4(OCH2CH2OCH3)10]

[Mn4Ti4( µ-Cl)2Cl6(OCH2CH2OCH3)12]

1 2

3

+ Sr

+ Ca- CpH- H2

+ Mn- CpH- H2

CH3OCH2CH2OH - CpH- H2

CH3OCH2CH2OH

CH3OCH2CH2OH

These results open an attractive opportunities for preparation of new highly reactive

compounds, which have not been prepared yet by other routs. Such complexes exemplifies an

atractive starting materials for a wide range of syntheses.

[1] E. I. Nagishi, A. Tongi, R. L. Halternman, Eds., The Metallocenes (Wiley-VCH:

Weinheim, 1998), Vol. 1, p. 282.

8/4/2008 S27 10:40 – 10:55

Synthesis, Structures and Reactions of

Chiral Titanocene and Zirconocene Complexes

Marcus Klahn, Perdita Arndt, Barbara Heller, Wolfgang Baumann, Anke Spannenberg, and

Uwe Rosenthal*

Leibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Str. 29a, D-

18059 Rostock, Germany

Organometallic complexes containing chiral ligands are important as catalytic or

stoichiometric mediators of enantioselective reactions [1]. So there was the approach to

synthesise group 4 metallocenes with chiral substituted cyclopentadienyl ligands. A good

example for this is the (-)-menthylcyclopentadienyl ligand [2]. Starting from the metallocene

dichlorides (1, 2) the alkyne complexes (3, 4)and the difluorides (5, 6) are formed. It was

possible to synthesise the so far unknown bis(8-phenylmenthylcyclopentadienyl)-

dichlorozirconium(IV) (7), which possibly provide a greater influence in stereoselectiv

reactions. This feasable influence is due to the phenyl-groups which tend to form -stacking

complexes [3]. Further reactions of these complexes, e.g. hydrosilylation of imines and the

formation of metallacycles, are under investigation.

M

MClCl

SiMe3

SiMe3- MgCl2

+ 2 Me3SnF MFF- 2 Me3SnCl

+ Mg,

(1) M = Ti(2) M = Zr

Me3SiC CSiMe3

(3) M = Ti(4) M = Zr

(5) M = Ti(6) M = Zr

(7)

[1] Halterman, R. L. Chem. Rev. 1992, 92, 965-994.

[2] a) Cesarotti, E.; Kagan, H. B.;Goddard, R.; Krüger, C. J. Organomet. Chem. 1978, 162, 297-309. b)

Gansäuer, A.; Narayan, S.; Schiffer-Ndene, N.; Bluhm, H.; Oltra, J. E.; Cuerva, J. M.; Rosales, A.; Nieger,

M. J. Organomet. Chem. 2006, 691, 2327-2331.

[3] Klahn, M.;Arndt, P.; Rosenthal U. unpublished results.

8/4/2008 S28 10:55 – 11:10

Unprecedented Si-C and C-H Activation Steps in the Formation of Hafnocene Alkyne Complexes

Stephan Peitz, Torsten Beweries, Vladimir V. Burlakov, Marc A. Bach, Perdita Arndt, Wolfgang Baumann, Anke Spannenberg, Uwe Rosenthal*

Leibniz-Institut für Katalyse e. V. an der Universität Rostock Albert-Einstein-Str. 29a, D-18059 Rostock, Germany

The chemistry of titanocene and zirconocene alkyne complexes Cp’2M(L)( 2-

Me3SiC2SiMe3) has been the subject of several reviews. These complexes play an

important role in many stoichiometric and catalytic reactions by generating the

corresponding metallocenes “Cp’2Ti” and “Cp’2Zr” under mild conditions [1].

HfCl

Cl

2 Li

- 2 LiCl

Hf

SiMe3

SiMe3

1Me3SiC2SiMe3

Figure 1. Interactions of Me3SiC2SiMe3 with Decamethylhafnocene.

Recently we reported on the synthesis of the first hafnocene alkyne complexes with an

intact starting alkyne, the compounds Cp*2Hf( 2-Me3SiC2SiMe3) (1) and

Cp2Hf(PMe3)( 2-Me3SiC2SiMe3) [2]. By simultaneous Si-C and C-H activation steps

during the synthesis of 1 two by-products 2 and 3 are formed, showing some unexpected

structural motifs [3].

[1] Rosenthal, U.; Burlakov, V. V. in: Titanium and Zirconium in Organic Synthesis (Ed.: I. Marek), Wiley-VCH 2002, 355.

[2] Beweries, T.; Burlakov, V. V.; Bach, A.; Arndt, P.; Baumann, W.; Spannenberg, A.; Rosenthal, U. Organometallics 2007, 26, 247.

[3] Beweries, T.; Burlakov, V. V.; Bach, M. A.; Peitz, S.; Arndt, P.; Baumann, W.; Spannenberg, A.; Rosenthal, U.; Pathak, B.; Jemmis, E. D. Angew. Chem. 2007, 119, 7031, Angew. Chem. Int. Ed. Engl. 2007, 46, 6907.

Hf CH

CSiMe3

SiMe3Hf

SiMe2

HSiMe3

2 3

8/4/2008 S29 11:10 – 11:25

Divergent Coordination Modes of Zinc Alkyls

Based on Various Pyrrolyl Ligands

Izabela Kraszewska,a Maciej Dranka,a Iwona Justyniak,b Janusz Lewi ski *,a

a Department of Chemistry, Warsaw University of Technology, Noakowskiego 3,

00-664 Warsaw, Poland b Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52,

01-224 Warsaw, Poland

The chemistry of organozinc compounds has a long history, in which many application for

metal alkyls have been found in both organic and organometallic chemistry. Over recent years

the exploitation of zinc complexes supported by -diketiminato ligand systems has provided a

number of spectacular results.[1]

As part of ongoing structure and reactivity studies involving the RZn(X,Y) chelate

complexes, we have initiated to examine the solid state and solution structure of alkylzinc

N,N’-chelate and N,O-chelate complexes based on pyrrolyl ligands. We turned our attention

to bi- and trifunctional pyrrolyl ligands, anticipating that a combination of pyrrole and Schiff

base type ligands or carbonyl group may provide spectacular results.

Series of zinc alkyl complexes supported by pyrrolyl ligands have been synthesized and

structurally characterized. Our studies demonstrate that pyrrolyl ligands are electronically

very flexible ligand system. For example, we have found that pyrrolylaldiminate type ligand

in zinc complexes shows -N or the dihapto 2- -donor type of coordination of pyrrolyl

ligand. the most diverse of coordination modes we have observed for zinc complexes

stabilized by 2,2’-dipirryl-diketone: the -N and the dihapto 2- -donor type for the pyrrolyl

unit and a double coordination of the carbonyl group.

The identification and characterization of weak intermolecular interactions as well as their

influence on the supramolecular structure of the studied complexes will be discussed.

[1] M. Cheng, D. R. Moore, J. J. Reczek, B. M. Chamberlain, E. B. Lobkovsky, G. W.

Coates, J. Am. Chem. Soc., 2001, 123, 8738.

9/4/2008 S30 9:05 – 9:20

Complexation of Sodium and Potassium Salts by Ditopic Hosts Based on

Organotin-substituted Crown Ethers

Alain Charly Tagne Kuate, a Gregor Reeske,a Markus Schürmann,a Klaus Jurkschat *a

aTechnische Universität Dortmund, Lehrstuhl für Anorganische Chemie II,

D-44221 Dortmund, Germany.

The central role played by cations and anions in physiology has provided the inspiration

for the design of abiotic receptors that bind selectively and simultaneously both ions. [1]. We

have synthesized receptors 1 - 4 and investigated their complexation properties. NMR studies

reveal the high potential of Ph2ClSn-CH2-[16]-crown-5[2], 1 , and Ph2ClSn-CH2-[19]-crown-6,

2, to complex NaSCN and KSCN, respectively , while in addition to NMR studies, X-ray

diffraction analyses showed that the robust receptors {Ph2(I)Sn-CH2-Sn(Ph)(I)-CH2-[16]-

crown-5}[3], 3, and {Ph2(I)Sn-CH2-Sn(Ph)(I)-CH2-[19]-crown-6, 4, overcome the lattice

energy of NaF in CD3CN and of KF in CDCl3 and bind these salts as separated ions to give

the ditopic complexes 3·NaF and 4·KF, respectively. Most recently, receptor 5 has been

synthesized and its complexation properties are currently investigated.

O

O

O

O

OSnPh

Ph

SCN

Cl

M

·

n

1 NaSCN, n = 12 KSCN, n = 2·

O

O

O

O OSnSn

II

PhPhPh

F M

n

3 NaF, n = 14 KF, n = 2··

I1

K1

Sn1

I2

Sn2

F1

O

OO

O

O

Sn

Sn

OO

I

II

I

O

5

[1] P. A. Gale, S. E. García-Garrido, J. Garric, Chem. Soc. Rev. 2008, 37, 151-190.

[2] G. Reeske, M. Schürmann, B. Costisella, K. Jurkschat, Organometallics, 2007, 26, 4170.

[3] G. Reeske, G. Bradtmöller, M. Schürmann, K. Jurkschat, Chem. Eur. J. 2007,13,10239.

9/4/2008 S31 9:20 – 9:35

C,N-chelated Organotin(IV) Fluorides

Petr Švec, Zde ka Pad lková, Aleš R ži ka

Department of General and Inorganic Chemistry, Faculty of Chemical Technology,

University of Pardubice, nám. s. legií 565, CZ-532 10, Pardubice, Czech Republic. E-mail:

[email protected]

Generally organotin(IV) fluorides tend to form oligo- or polymeric species with 2D and

3D structures connected via fluorine bridges and thus to saturate their tin coordination

vicinity/number up to seven. These species often with changeable composition, structure and

properties are not useful in synthetic or catalytic applications.

To prevent the formation of polymeric species, we decided to saturate the tin coordination

sphere by adjacent donor atom. For such a duty we have selected the 2-(N,N-

dimethylaminomethyl)phenyl group as a C,N-chelating ligand (LCN) which was frequently

studied in the literature [1].

The structure, reactivity and use of some C,N-chelated organotin(IV) fluorides will be

discussed.

Fig. 1: The molecular structure of two isomers of [LCN(n-Bu)SnF2]n

[1] Jastrzebski, J. T. B. H.; van Koten, G.: Adv. Organomet. Chem. 1993, 35, 241, and

references cited therein.

9/4/2008 S32 9:35 – 9:50

Intramolecularly coordinated heteroleptic stannylenes:

Syntheses and Structures

Vajk Deákya, Markus Henna, Markus Schürmanna, Bernhard Mahieub und Klaus Jurkschat*,a,aLehrstuhl für Anorganische Chemie II, Technische Universität Dortmund,

D-44221, Dortmund, Germany bLaboratoire de Chimie Physique Moléculaire et de Cristallographie (CPMC)

B-1348 Louvain-la-Neuve, Belgium

In course of our systematic studies on heavy carbene-analogues [1] and related compounds

[2], we herein present results concerning (i) configurational stability of the intramolecularly

coordinated heteroleptic stannylenes 1-4, (ii) reaction of 1-4 with chalcogenes providing the

four-membered rings 5-12, (iii) synthesis, structure and reactivity of the stannylene transition

metal complexes 13-16, and (iv) the first heteroleptic stannylene ruthenium complex 17.

13, M = Pd, X= Cl14, M = Pd, X = Br15, M = Pd, X = I 16, M = Pt, X = Cl

5; X = SPh, E = O6; X = Cl, E = O7; X = Cl, E = S8; X = Br, E = S9; X = l, E = S

10; X = Cl, E = Se11; X = Br, E = Se12; X = l, E = Se

P

P

t-Bu

RO ORO

ROOR

O

SnX

1, X = Cl2, X = Br3, X = I4, X = SPh

SnEE

SnX

XR R

MSn

XSn

X

Cl ClRR

RuSnR ClCl17

Insights into configurational stabilityof 1-4 depending on X

chalcogen

MX2

R = iPr

Cl

Sn XR

[1] Henn, M.; Schürmann, M.; Mahieu, B.; Zanello, P.; Cinquantini, A.; Jurkschat, K.

J. Organom. Chem. 2006, 691, 1560 and references cited therein.

[2] Jambor, R.; Kašná, B.; Kirschner, K.N.; Schürmann, M.; Jurkschat, K. Angew. Chem.

2008, in press

9/4/2008 S33 9:50 – 10:05

Structure and reactivity of transition metal complexes containing the heteroleptic organostannylene 2,6-(Me2NCH2)2C6H3SnCl

J. Martincová,a R. Jambor,a M. Schürmannb, K. Jurkschatb

a Department of General and Inorganic Chemistry, Faculty of Chemical Technology,

University of Pardubice, nám. s. legií 565, CZ-532 10, Pardubice, Czech Republic.bLehrstuhl für Anorganische Chemie II der Technischen Universität Dortmund, D-44227

Dortmund, Germany.

In course of a systematic study on the reactivity of heteroleptic organostannylenes [1,

2] reactions of the heteroleptic stannylene 2,6-(Me2NCH2)2C6H3SnCl (RSnCl) [3] with

selected transition metal derivatives (TM) are reported. These reactions provided a variety of

novel complexes R(Cl)Sn-TM (Fig.1). In the latter complexes the stannylene is a two-

electron-donor ligand.

The preparation, structure and reactivity of these complexes will be discussed.

NMe2

Me2N

SnCl

TM

Fig. 1:

[1] (a) Mehring, M.; Löw, C.; Schürmann, M.; Uhlig, F.; Jurkschat, K. Organometallics 2000,

19, 4613. (b) Henn, M.; Schürmann, M.; Mahieu, B.; Zanello, P.; Cinquantini, A.; Jurkschat,

K. J. Organomet. Chem. 2006, 691, 1560.

[2] Martincova, J.; Dostal, L.; Ruzicka, A.; Taraba, J.; Jambor, R.: Organometallics 2007, 26

4102-4104.

[3] Jastrzebski, J. T. B. H.; van Koten, G.; Knaap, C. T.; Schreurs, A. M. M.; Kroon, J.; Spek,

A. L. Organometallics 1986, 5, 1551.

9/4/2008 S34 10:25 – 10:40

1,1’-Diphosphaferrocenyl conjugates of aminoacid esters

Bartosz Mucha, Janusz Zakrzewski

Department of Organic Chemistry University of Lodz 90-136 Lodz, Narutowicza 68

There has been considerable interest in the introduction of redox-active ferrocenyl groups

into natural aminoacids, peptides or proteins [1]. One of the most important methods of

synthesis of ferrocenyl conjugates of aminoacids is the reaction of ferrrocenecarboxaldehyde

(FcCHO) with aminoacid esters, giving corresponding imines, reduced in situ to

FcCH2NHCH(R)COOR’. Recently we became interested in the application of this approach

for synthesis of 1,1’-diphosphaferrocenyl conjugates of aminoacids from aldehyde 1.

However, this aldehyde is planary chiral and the use of the racemic compound would lead to

mixtures of diastereomers. Fortunately, we earlier described an efficient method of resolution

of this compound [2] and herein we report on synthesis of stereoisomers 2 and 3 from

glycine, L-alanine and L-phenylalanine methyl esters. We have also found that 2a reacts with

one eq. of W(CO)5(THF) to give mixtures of complexes 4-6, which were separated by

column chromatography and their structures were confirmed by spectroscopic data.

PMe Me

CHO

P

Me MeFe

PMe Me

OHC

P

Me MeFe

1

PMe Me

NH H

R

COOMe

P

Me MeFe

P

Me Me

NH

H

R

COOMe

P

Me MeFe

F

2 a-c 3 a-c

(a) R=H(b) R=Me(c) R=CH2Ph

PMe Me

NH COOMe

P

Me MeFe W(CO)5

W(CO)5

PMe Me

NH COOMe

P

Me MeFe

W(CO)5

PMe Me

NH COOMe

P

Me MeFe W(CO)5

4 5 6

(1) Van Staveren, D. R.; Metzler-Nolte, N. Chem. Rev, 2004, 104, 5931-5985

(2) K ys, A.; Zakrzewski, J.; Jerzykiewicz, L. Tetrahedron: Asymmetry, 2003, 14, 3343-3346

9/4/2008 S35 10:40 – 10:55

Synthesis of bimetallic complexes with nickelafluorenyl ring

El bieta Kami ska, Piotr Buchalski, Antoni Pietrzykowski*

Warsaw University of Technology, Faculty of Chemistry,

Noakowskiego 3, 00-664 Warsaw, Poland

The aim of this work was to optimize synthesis of nickelafluorenyllithium and to study

reactions of this compound with iron and cobalt acetylacetonates. The first part of the work

was to synthesize nickelafluorenyllithium in various solvents. Reactions carried out in two of

the applied solvents (diethyl ether and tetrahydrofurane) gave satisfactory results. The

reaction carried out in diethyl ether was more effective. The yield of the product was higher

and less reaction steps were needed to get the final compound.

CpNi(Et2O)2Li

+ Cp2NiEt2O + CpLi

Li Li

+DME

2 Et2O

Li(DME)

CpNi

In the second part of this work the reactions of nickelafluorenyllithium with iron(II)

acetylacetonate and pentamethylcyclopentadienylcobalt(II) acetylacetonate were studied. In

the first reaction bimetallic complex (nickel – iron) was not formed.

In the second reaction the new bimetallic complex, with both cobalt and nickel atoms, was

formed. The EI mass spectrum of the complex 1 showed its molecular ion at m/e 469 with an

isotopic pattern characteristic for one nickel atom in a molecule. The molecular structure of

the complex 1 was determined by X-ray diffraction analysis.

+ Cp*Co(acac) + Li(acac) + DMEEt2O

CpNi

Li(DME)

CpNi

CoCp*

1

9/4/2008 S36 10:55 – 11:10

REACTION OF NICKELOCENE WITH METHYLLITHIUM IN THE PRESENCE OF OLEFINS

Beata Herbaczy skaa, Antoni Pietrzykowski*,a, Lucjan B. Jerzykiewiczb

aWarsaw University of Technology, Faculty of Chemistry, Koszykowa 75, 00-662 Warsaw, Poland aUniversity of Wroc aw, Faculty of Chemistry, Joliot-Curie 14, 50-353 Wroc aw, Poland

Nickelocene reacts with organolithium and –magnesium compounds (LiR, RMgX) form-

ing in the first step an unstable 16 VE species {CpNiR}. This species undergoes further reac-

tions: hydrogenation, coupling, elimination etc., forming a wide range of cyclopentadienyl-

nickel clusters. The main product of the reaction of nickelocene with methyllithium is

ethylidyne-tri(cyclopentadienylnickel) cluster (NiCp)3( 3-CCH3). The other products isolated

at lower yield were: -allyl complex (NiCp)( 3-C5H7), di(cyclopentadienylnickel) complex

(NiCp)2( -C5H6), and clusters (NiCp)3( 3-CH), (NiCp)5( -CCH3), (NiCp)6 , (NiCp)6C,

(NiCp)6C2. The reaction of nickelocene with methyllithium carried out in the presence of ole-

fins allowed for isolation of the -complex CpNi(Me)( 2-alkene). This complex, stable below

0 ºC, undergoes slow thermal decomposition at room temperature, forming the same products

as in the previous reaction. The main product was also the cluster (NiCp)3( 3-CCH3).[1,2,3]

However, the main product of the reaction of methyllithium with nickelocene derivative,

bearing alkenyl substituents in the cyclopentadienyl rings, was the dinickel compound of the

structure shown below:

+ MeLiNi

Si

Si

Intramolecular stabilization of the dinickel compound by the formation of olefinic com-

plex with nickel, appeared to be strong enough to prevent the formation of higher clusters in

consequent reactions.

[1] S. Pasynkiewicz, W. Buchowicz, A. Pietrzykowski, Transition Met. Chem. 23 (1998) 301

[2] S. Pasynkiewicz, A. Pietrzykowski, Coordination Chemistry Reviews 231 (2002) 199

[3] W. Buchowicz, K. Star ga, A. Pietrzykowski, L. B. Jerzykiewicz, J. Organomet. Chem. 690 (2005) 1192

9/4/2008 S37 10:10 – 11:25

Group IV and V metal complexes of the (NOSON)- and (ONNO)- type

ligands; synthesis, structure and catalytic activity

Izabela Ja yna, Piotr Sobota, Zofia Janas*

Faculty of Chemistry, University of Wroc aw, 14, F. Joliot-Curie, 50-383 Wroc aw, Poland.

One of the most significant application of group IV metal complexes is the catalytic

polymerization of -olefins. In recent years there is a growing recognition that

nonmetallocene complexes hold great promise as olefin polymerization catalysts [1]. Most

successful developments in terms of catalysis have appeared using chelating, polydentate

bis(aryloxide) ligands having an additional coordinating heteroatom (N, O, S).

Recently we have described the family of titanium complexes based on the 2,2’-thiobis{4-

(1,1,3,3-tetramethylbutyl)phenolato} (OSO) ligand, which led after activation with aluminum

alkyls to highly active, well-defined, single-site catalysts to ethene polymerization process

[2]. As a part of our ongoing study on this area we were interested in modification of the

(OSO) ligand with additional heteroatom like nitrogen to achieve new ligands of the

(NOSON)- and (ONNO)- type (Scheme) and their application to generation of group IV and

V metal complexes that might serve as catalysts for olefin polymerization process. Synthesis

of two new ligands and their Ti, Ta, Nb complexes will be presented in details.

OH

CH3CH3

CH3CH3

CH3

S

OH

CH3 CH3

CH3CH3

CH3

+ 2 NH2tBu + 2 HCHO

ethanol

OH

CH3CH3

CH3CH3

CH3

S

NH

CH3CH3

CH3OH

CH3 CH3

CH3CH3

CH3

NH

CH3 CH3

CH3

- 2H2O

OH

CH3CH3

CH3CH3

CH3

2 + NH2CH2CH2N(CH3)2 + 2 HCHO

OH

CH3CH3

CH3CH3

CH3

N

OH

CH3 CH3

CH3CH3

CH3

NCH3 CH3

- 2H2O

ethanol

(OSO)H2 (NOSON)H4 (ONNO)H2

[1] (a) Britowsek, G. J. P.; Gibson, V. C.; Wass, D. F., Angew. Chem., Int. Ed. 1999, 38, 428. (b) Gibson, V. C.;

Spitzmesser, S. K., Chem. Rev. 2003, 103, 283.

[2] (a) Janas Z.; Jerzykiewicz L. B.; Przybylak K.; Sobota P.; Szczegot K.; Wi niewska D., Eur. J. Inorg. Chem.,

2005, 1063-1070. (b) Janas Z.; Jerzykiewicz L. B.; Sobota P.; Szczegot K.; Wi niewska D., Organometallics,

2005, 24, 3987-3994. (c) Wi niewska D.; Janas Z.; Sobota P.; Jerzykiewicz L. B., Organometallics, 2006,

25(26); 6166-6169.

9/4/2008 S38 11:25 – 11:40

1,1,2,2,3,3,4-Hepta-tbutyl-4-magnesio-chloro-tetrastanna-cyclobutane: synthesis and reactions

M. Lechner,a K.Decker,a R.Fischer,a F.Uhlig*,a

aInstitute of Inorganic Chemistry, Graz University of Technology, Stremayrgasse16, A-8010,

Graz, Austria

Magnesio- tin compounds are reactive intermediates for the synthesis of cyclic organo-

tin products that are inaccessible by other synthetic pathways. [1]

1,1,2,2,3,3,4-Hepta-tbutyl-4-magnesio-chloro-tetrastanna-cyclobutane (1) can be

synthesised starting either from di-tert-butyldichlorostannane or from octa-tert-

butyldichlorotetrastannane in a Grignard type reaction. This product is fully characterised by

multinuclear NMR spectroscopy (119Sn, 1H and 13C) Due to its nucleophilicity 1 is an

interesting starting point for further derivatisation reactions.

Sn

Sn Sn

Sn

Mg

Cl

1

Among the resulting products synthesised are tBu7Sn4Me, tBu7Sn4Pr and tBu7Sn4Br.tBu7Sn4Me could be characterized by X-ray crystal structure analysis.

This presentation deals with a description and comparison of the two different ways to

obtain 1,1,2,2,3,3,4-hepta-tertbutyl-4-magnesio-chloro-tetrastanna-cyclobutan. Furthermore

some reaction of compound 1 will be discussed as well.

[1] R.Fischer, F.Uhlig, Coord.Chem.Rev., 2005, 249(19-20), 2075-2093

9/4/2008 S39 13:35 – 13:50

Investigating the catalytic hydrogenation with rhenium(I) nitrosyl complexes

B. Dudlea, H. Berkea*

aInstitut of inorganic chemistry, university of Zürich, Winterthurerstrasse 190, 8057 Zürich, Switzerland

Catalytic hydrogenations belong to the standard tools of synthetic organic chemistry.

Nevertheless there are only rare examples of non noble metal based catalysts for such

reactions. Our research interest is therefore focused on the development of new rhenium

based catalysts for hydrogenation. Recently the rhenium-nitrosyl complexes [ReH2( 2-

C2H4)(NO)(PR3)] and [ReH( 2-BH4)(NO)(PR3)] (R=isopropyl, cyclohexyl) have successfully

been used as hydrogenation and hydrosilylation catalysts[1],[2]. It was anticipated that these

catalyst precursors lose initially the weakly bound ligand (C2H4 or BH3) and the catalytic

cycle then follows than a typical Wilkinson-type mechanism:

PPh3

Re

PPh3

ON ClPh3P

H -PPh3

+PPh3

PPh3

Re

PPh3

ONHCl

PPh3

Re

PPh3

ON ClH-C2H4

+C2H4

+C2H4-C2H4

PPh3

Re

PPh3

ON HCl

PPh3

Re

PPh3

ONCl

PPh3

Re

PPh3

ONClHH

PPh3

Re

PPh3

ONClH

+H2

-H2-C2H6

+C2H4

-C2H4

Challenged by these results we investigated other, similar complexes and found, that also

[ReH2(NO)(PPh3)3], [ReHCl(NO)(PPh3)3] and [ReHCl(C2H4)(NO)(PPh3)2] complexes

catalyse the hydrogenation of the model substrates ethylene, 1-hexene and cyclohexene.

Therefore we study these reactions in greater detail to obtain experimental data to confirm the

proposed mechanism and also to get further information on the optimization of the catalyst.

1 A. Chualeb, H.W. Schmalle, H. Berke to be published 2 Y. Jiang, H. Berke, chem. Comm. 2007, 37, 3571-3573

9/4/2008 S40 13:50 – 14:05

High-Selective Dehydrogenative Silylation Catalyzed by Rhenium

Complexes: Reaction Development and Mechanistic Studies

Yanfeng Jiang, Christian M. Frech, Olivier Blacque, Fox Thomas, Heinz Berke*

Anorganisch-chemisches Institut, Universität Zürich, Winterthurerstr.190, CH-8057 Zürich,

Switzerland.

Dehydrogenative silylation reaction, which permits the direct production of unsaturated

silyl compounds from olefins and silanes, has drawn increasing attention during the last two

decades.1 However, a major drawback of this reaction is the formation of hydrosilylated by-

products. Thus, highly chemoselective processes are desired. So far, catalysts for selective

dehydrogenative silylation are mainly limited to late transition metal complexes, such as

[M3(CO)12] (M = Fe, Ru, Os),2 cationic [Rh(COD)2]BF4/PPh3,3 [RuH2(H2)2(PCy3)2] 4 and

cationic Pd(II) complexes 5.


R'3Si H + R121.0 mol% [Re]

toluene R'3Si

H

H

R1

R'3Si

R1+ + R1


We would like to report rhenium(I) complexes [Re(Br)2(NO)(PR3)2(L)] (L = H2 1, CH3CN

2 and ethylene 3; R = iPr a and Cy b) 6 catalyzed highly selective dehydrogenative silylation

of substituted styrenes with silanes. Mechanistic studies were carried out, which shed a light

into the initial reaction path and the catalytic cycle. Extension of these studies concern

obtaining more active rhenium complexes applying ligand tuning.

[1] Marciniec, B. Coord. Chem. Rev. 2005, 249, 2374.

[2] (a) Seki, Y.; Takeshita, K.; Kawamoto, K.; Murai, S.; Sonoda, N. J. Org. Chem. 1986, 51,

3890. (b) Kakiuchi, F.; Tanaka, Y.; Chatani, N.; Murai, S. J. Organomet. Chem. 1993, 456,

45.

[3] Takeuchi, R.; Yasue, H. Organometallics. 1996, 15, 2098

[4] Christ, M. L.; Sabo-Etienne, S.; Chaudret, B. Organometallics. 1995, 14, 1082

[5] LaPointe, A. M.; Rix, F. C.; Brookhart, M. J. Am. Chem. Soc. 1997, 119, 906.

[6] Jiang, Y.; Berke, H. Chem. Commun. 2007, 3571.

9/4/2008 S41 14:05 – 14:20

Silylative coupling of terminal alkynes with vinylsilicon compounds

catalyzed by ruthenium complexes

Beata Dudziec, Bogdan Marciniec*

Adam Mickiewicz University, Faculty of Chemistry, Department of Organometallic

Chemistry, Grunwaldzka 6, 60-780 Pozna , Poland

Substituted alkynylsilanes are an important group of reagents commonly used in many

fields of chemistry, e.g. as alkynylating agents in synthesis of organic, organosilicon and

natural products as well as precursors of optoelectronic materials[1]. Alkynylsilanes can be

prepared by classical stoichiometric routes or by metal complex – catalyzed reactions[2].

Herein, we present a new catalytic silylative coupling reaction of terminal alkynes with

vinyl-substituted organosilicon compounds proceeding in the presence of ruthenium

complexes. It is an efficient and direct way for the synthesis of substituted alkynylsilanes[3].

R H SiR'3+[Ru] (1-2 mol%)

R SiR'3

R = alkyl, silyl, germylR' = alkyl, aryl, alkoxyl

toluene

50 - 100%-

This process can be employed for modification of multivinylsubstituted silicon

compounds since monoalkynyl-substituted products are obtained selectively. The mechanism

of this particular (sp)C-H activation based on the stoichiometric reactions of catalyst with

substrates and DFT calculation methods has been discussed.

[1] Greene, T.W.; Wuts, P.G.M. Protective Groups in Organic Synthesis, Wiley, New York,

1999; Sudo, T.; Asao, N.; Yamamoto, Y. J. Org. Chem. 2000, 65, 8919-8923; Fiandanese,

V.; Bottalico, D.; Marchese, G.; Punzi, A. Tetrahedron 2006, 62, 5126; Hübner, H.;

Haubmann, Ch.; Utz, W.; Gmeiner, P. J. Med. Chem. 2000, 43, 756

[2] Fletcher, M. D. in Comprehensive Organic Functional Group Transformations, Vol. 2

(Eds.: Katritzky, A. R.; Taylor, R. J. K.), Elsevier, Oxford, 2005, pp. 1181-1189

[3] Marciniec, B.; Dudziec, B.; Kownacki, I. Angew. Chem. Int. Ed. 2006, 45, 8180;

Marciniec, B.; awicka, H.; Dudziec, B. J. Organomet. Chem. 2008, 693, 235

9/4/2008 S42 14:20 – 14:35

New catalytic route to boryl- and borylsilyl substituted buta-1,3-dienes

J drzej Walkowiak, Magdalena Jankowska-Wajda, Bogdan Marciniec*

Department of Organometallic Chemistry, Faculty of Chemistry, A.Mickiewicz University,

Grunwaldzka 6, 60-780 Pozna , Poland, e-mail: [email protected]

Dienylboronates and dienylsilylboronates constitute a class of functionalized building

blocks commonly used in organic and natural products synthesis, since the boronate moiety,

as well as silyl group, can be easily converted into other functional groups [1,2].

Borylsubstituted buta-1,3-dienes can be prepared by classical stoichiometric routes using

organometallic reagents or more recently by catalytic methods.

In the communication we report a new convenient method for selective synthesis of 1-

boryl and 1-boryl-4-silyl substituted buta-1,3-dienes via one step coupling of terminal alkynes

(also silylacetylenes) with vinylboronates catalyzed by complexes containing [Ru]-H bond,

occurring according to the following equitation:

BO

O=

OB

O

O

OB ,

O

OB + R

[Ru-H]

R

+ RO

OB

O

OB

The stoichiometric reactions were carried out to prove the mechanism of this new process,

in which insertion of terminal acetylene to [Ru]-H bond is the preliminary step followed by

insertion of vinylboronate to Ru-C= bonds and elimination of boryl dienes. It is in contrast to

previously recognized reactions of acetylenes with vinylsilanes and vinylgermanes, which

occur via preliminary insertion of vinylmetalloid into M-H bond to give M-E bond (and

ethylene) followed by insertion of acetylene into M-E bond and elimination of silyl and

germyl functionalized ethynes [3,4].

[1] Thirsk C., Whiting A., J. Chem. Soc., Perkin Trans. 1, 2002, 8, 999

[2] Coleman R. S., Walczak M. C., Organic Lett., 2005, 7, 2289

[3] Marciniec B., Dudziec B., Kownacki I., Angew. Chem., Int. Ed., 2006, 45, 8180

[4] Marciniec B., awicka H., Dudziec B., Organometallics, 2007, 26, 5188.

9/4/2008 S43 14:55 – 15:10

Oligonuclear Ethenyl Bridged Styryl Complexes of Ruthenium: Synthesis, Electrochemical and Spectroeletrochemical Investigation

Michael A. Linseis, Rainer F. Winter* Institut für Anorganische Chemie der Universität Regensburg, Universitätsstraße 31, 93053,

Regensburg, Germany J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of the Czech Republic,

Dolejškova 3, Prague, Czech Republic

The Ru-vinyl entity exhibits strong delocalization of the redox orbitals over the metal as

well as the organic bridging ligand [1]. Although “non-innocent” behaviour is well known for

inorganic coordination compounds, there are only few examples of organometallic systems

with direct metal-carbon bonds. Recently the electrochemical behaviour of mononuclear

ruthenium-vinyl-complexes has been studied in a systematic way to link the metal vs. ligand

contribution to experimentally accessible values like half-wave potentials, oxidation induced

CO band shifts and ESR-parameters [2]. We have now extended our studies to di- and

tetranuclear stilbene and tetraphenylethene derived complexes [{RuCl(CO)(PR´3)2L}2{µ2-

bis(styryl)ethene}] and [{RuCl(CO)(PR´3)2L}4{µ4-tetrakis(p-styryl)ethene}] (R´ = Ph, iPr, Et;

L = none or ethyl isonicotinate). The complexes were investigated by electrochemistry, IR-

and UV/Vis/NIR-spectroelectrochemistry and ESR-spectroscopy in order to probe for the

degree of electron delocalization in their various oxidized forms and the relative metal and

ligand contributions to the respective redox orbitals. These studies also revealed strong

electrochromism, particularly of the tetranuclear complexes. Our experimental results are

backed by quantum chemistry.

[1] J. Maurer, B. Sarkar, B. Schwederski, W. Kaim, R. F. Winter, S. Záliš, Organometallics 2006, 25, 3701. J. Maurer, M. Linseis, B. Sarkar, B. Schwerderski, M. Niemeyer, W. K[2] aim, S. Záliš, C. Anson, M. Zabel, R. F. Winter, J. Am. Chem. Soc. 2008, 130, 259.

9/4/2008 S44 15:10 – 15:25

Styryl complexes of Ruthenium and Osmium as Probes for

Electron Transfer Across Multiple Hydrogen Bridges

Markus Pichlmaier,a Stanislav Zálišb and Rainer F. Winter*,a

a) Institut für Anorganische Chemie, Universitätsstraße 31, 93040, Regensburg, Germany b) J. Heyrovský Institute of Physical Chemistry v.v.i, Academy of Sciences of the Czech

Republic, Dolejškova 3, 182 23 Prague 8, Czech Republic

Electron transfer is one of the most fundamental processes in chemistry and biology. The spatial organization of electron donor and acceptor sites in enzymes and artificial supramolecular systems often depends on strong hydrogen bridges. A quadruply hydrogen bonding, symmetrical DDAA motif based on ureapyrimidones has recently been shown to efficiently mediate electron transfer between two ferrocenyl substituents[1]. We here discuss the synthesis, structures, solution behaviour and the electron transfer properties of ureapyrimidone dimers 2a,b and 3a (see Chart) having redox active ruthenium and osmium styryl substituents in their backbones. This general structure ensues a high charge and spin density at the styryl group in the oxidized state(s) [2], while the carbonyl ligand of complexes 2a,b and 3 provides an indicative, charge-sensitive spectroscopic label. Both these attributes are missing in the ferrocenyl substituted counterpart.

N

N

HO

NO

OR

R

NH H

N

N

HO

N O

ORR

NHH

C

C

C

C

H

H M COCl

PiPr3

iPr3P

H

HMiPr3P

PiPr3ClOC

R = nBu, M = Ru: 2a; M = Os: 3aR = allyl, M = Ru: 2b

O

N NH H

CC

H

H Ru CO

Cl

PiPr3

PiPr3

C

5

The issue of the presence and strength of electronic interactions between the two identical styryl units is addressed by in situ IR and UV/Vis/NIR spectroelectrochemistry. The results on the ureapyrimidone-bridged dimers are compared to those for the phenylurea substituted styryl ruthenium complex 5, which is monomeric in solution. Quantum chemical calculations performed on simplified model complexes aid in the interpretation of our experimental results.

[1] H. Sun, J. Steeb, A. E. Kaifer, J. Am. Chem. Soc. 2006, 128, 2820. [2] J. Maurer, M. Linseis, B. Sarkar, B. Schwerderski, M. Niemeyer, W. Kaim, S. Záliš,

C. Anson, M. Zabel, R. F. Winter, J. Am. Chem. Soc. 2008, 130, 259.

9/4/2008 S45 15:25 – 15:40

Synthesis, characterization and properties investigation of tungsten and

molybdenum hydrides.

A. Dybov, O. Blacque, T. Fox, C. Frech, H. Berke*

Anorganisch-Chemisches Institut der Universität Zürich, Winterthurerstrasse 190, 8057 Zürich,

Switzerland

The hydrogenation of C=O double bonds of ketones and aldehydes play an important role in

the agricultural, pharmaceutical and other chemical industries. Up to now, most of the homogeneous

catalysts promoting this reaction are based on precious metals, such as ruthenium and rhodium.

Tungsten and molybdenum hydride complexes were shown to provide hydride transfers to ketones

that is the first step in a hypothetical catalytic cycle of the hydrogenation reaction [1,2]. The ligand

trans to the hydrogen atom has a crucial influence on its activity.

We report the synthesis of 1,2 – bis(diisopropylphosphino)ethane molybdenum and tungsten

hydride complexes with NO:

M

NO

H

P

P

P

P

M = W, Mo

In addition, we discuss reactions which show the chemical properties of the corresponding

hydrides. The temperature dependent 2H T1 experiments have been done, that allowed to calculate of

T1 min and estimate the ionicity of M – D bond.

Catalytic hydrogenation experiments are on going and respective results will be reported.

[1] J. Cugny, H. W. Schmalle, T. Fox, O. Blacque, M. Alfonso, H. Berke, Eur. J. Inorg.

Chem. 2006, 540–552

[2] F. Furno, T. Fox, H. W. Schmalle, H. Berke, Organometallics, Vol. 19, No. 18, 2000

9/4/2008 S46 15:40 – 15:55

New macrocyclic complexes of copper and nickel –

on the network and charge density topologies

Rados aw Kami ski,a,b Pawe led ,b S awomir Domaga a,b

Bohdan Korybut-Daszkiewicz,c Krzysztof Wo niak*,a

aDepartment of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664

Warsaw, PolandbDepartment of Chemistry, Warsaw University, Pasteura 1, 09-093 Warsaw, PolandcInstitute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224

Warsaw, Poland

Macrocyclic complexes of copper and nickel are very interesting and vigorously studied

building blocks for new molecular machines precursors design and synthesis. So far these

moieties have been applied in i.e. preparation of electrochemically controlled molecular

shuttle [1], and further studies on them are currently under way.

Here we report the structural and experimental charge density analyses of new model

macrocyclic and bis-macrocyclic [2] copper and nickel complexes, which may be potentially

applied in synthesis of molecular machines and crystal engineering.

[1] B. Korybut-Daszkiewicz, A. Wi ckowska, R. Bilewicz, S. Domaga a, K. Wo niak,

Angew. Chem. Int. Ed., 2004, 43, 1668-1672,

[2] M. Gali ska, B. Korybut-Daszkiewicz, U. E. Wawrzyniak, R. Bilewicz, P. led , R.

Kami ski, P. Dominiak, K. Wo niak, Eur. J. Inorg. Chem., in print.

10/4/2008 S47 8:35 – 8:50

Organometallic Complexes Supported by Bis(imidazolin-2-imino)pyridine

Pincer Ligand and by Chiral Ligand

Sabina Filimon, Dejan Petrovic, Tarun K. Panda, Matthias Tamm*

Institut für Anorganische und Analytische Chemie, Technische Universität Carolo-

Wilhelmina zu Braunschweig, Hagenring 30, 38106, Braunschweig, Germany

Since Brookhart’s and Gibson’s concurrent discovery in the 1990s that late transition

metal complexes of the Schiff base 2,6-bis(imino)pyridine ligands are exceptionally active

olefin polymerization catalysts [1,2], these pincer-type ligands have attracted a lot of attention

[3]. Recently, we have introduced the tridentate bis(imidazolin-2-imino)pyridine ligand

(TLtBu) and its application in copper coordination chemistry [4]. The TLtBu ligand can be best

described by the two limiting resonance structures A and B (Scheme 1) and can be considered

as a potentially more basic analogue of Schiff base 2,6-bis(imino)pyridine ligands [3]. Due to

the highly basic nature of the ligand, it can stabilize a number of Lewis acidic metal ions.

BA

N

N NN

N N

N

N

N NN

N N

N

TLtBu

Scheme 1

The interesting results reported for dioxygen activation with related guanidine copper

complexes encouraged a reactivity study of the cationic copper(I) complex towards dioxygen

or other oxygenating agents. Important discoveries have also been made in the field of

lanthanide (III) coordination chemistry with multidentate ligands. To gain insight into the

ligand behavior towards lanthanides, the reaction of TLtBu with LnCl3 was studied, and the

synthesis of cationic lanthanide alkyl complexes was attempted.

[1] S. D. Ittel, L. K. Johnson, M. Brookhart, Chem. Rev. 2000, 100, 1169.

[2] V. C. Gibson, C. Redshaw, G. A. Solan, Chem. Rev. 2007, 107, 1745.

[3] M. Albrecht, G. van Koten, Angew. Chem. Int. Ed. 2001, 40, 3750.

[4] D. Petrovic, T. Bannenberg, S. Randoll, P.G. Jones, M. Tamm, Dalton Trans.2007, 2812.

10/4/2008 S48 8:50 – 9:05

Toward Synthesis of Hybrid Ligands – Regioselective Phosphination of

Carbaporpholactone.

Norbert Grzegorzek, Mi osz Pawlicki, Lechos aw Latos-Gra y ski*,

Department of Chemistry, University of Wroclaw, 14 F. Joliot-Curie St/, Wroclaw 50-383,

Poland

Carbaporphyrinoids are porphyrin analogues containing a CH fragment instead of one

of the pyrrolic nitrogens. This so called “internal carbon” is often found susceptible to

substitution reactions. Examples reported to date include alkylations, halogenations, nitration,

internal fusion, acetoxylation, cyanation, oxygen insertion, regioselective pyridination. and

formation of a ketal Recently reported carbaporpholactone 1 provides a suitable

environment to stabilize the rare oxidation states (copper(III) or silver(III)) of coordinated

metal ions due the formation of -metal-carbon bond. Regioselective reaction of silver(III)

carbaporpholoactone with potassium diphenylophosphide in THF yields 21-

(diphenylphosphino)-carbaporpholactone 2 as the single substitution product which in

oxidative reaction conditions transforms quantitatively into 21-(diphenylphosphoryl)-

carbaporpholactone 3 as confirmed by detailed NMR studies. A mechanism involving a high-

valent silver complex is proposed for the phosphination reaction.

NH

N

NH

OO

PhPh

p-Tol p-Tol

NH

N

NH

OO

PhPh

p-Tol p-Tol

PPh PhAcOAg (Ph)2PK

Ag N

N

N

OO

PhPh

p-Tol p-Tol

III

1 1-Ag 2

NH

N

NH

OO

PhPh

p-Tol p-Tol

PPh

O

Ph

3

[O]

The structure of copper(II) of 21-(diphenylphosphoryl)-carbaporpholactone 3-Cu has been

determined at 173 K by X-ray diffraction: 3-Cu presents unique features related to the hybrid

nature of 3. The copper(II) is five-coordinate with bonds to three pyrrolic nitrogens, the

oxygen atom of phosphoryl moiety, and to the pyrrole C(21) carbon. Further aspects of the

reactivity of carbaporpholactone complexes are currently explored in our laboratory.

10/4/2008 S49 9:05 – 9:20

Helical Porphyrinoids: Incorporation of Ferrocene Subunits into

Macrocyclic Structures

Irena Simkowa, Marcin St pie , Lechos aw Latos-Gra y ski

Department of Chemistry University of Wroc aw, 14 F. Joliot-Curie St., 50-383 Wroc aw,

Poland

Ferrocene-containing porphyrinoids have been synthesized, in which ferrocene-1,1'-diyl

units are linked to a dipyrrin 2a and 2b, dicarbabilane 3b or thiatripyrrin 5 to form

macrocyclic structures.

FeHN

NFe

HN

HNAr

ArH

Fe S

N

NTol

Tol

1. ArCHO, BF3·Et2O2. DDQ (1 equiv)

Fe

NH

NH

5 (9%)

S

Tol

Tol

HO

HO

1. CH2Cl2, BF3·Et2O2. Et3N3. DDQ (2 equiv)

4

+Fe

NH

NH

1

2a Ar = Ph (8%)2b Ar = C6F5 (34%) 3b Ar = C6F5 (1%)

1

NMR spectroscopic evidence shows that these new systems, adopt helical conformations,

which undergo an inversion process in solution. The helical conformation of 2 was confirmed

by X-ray diffraction. Moreover, small amounts of unexpected scrambling products have been

isolated and characterized, namely a dipyrrin-bisferrocenophane and two expanded bis-

ferrrocene macrocycles. Formation of these systems, which contain macrocyclic rings of

different sizes, is a consequence of the structural flexibility of the ferrocene unit. Cyclic

voltammetry demonstrates that ferrocene oxidation is reversible in all systems reported here,

and that it is finely tuned by the properties of the macrocyclic system.

10/4/2008 S50 9:40 – 9:55

A New Class of Imidazole based N,N,O Ligands:

Synthesis, Structure and Reactivity

Nina Fischer,a Liv Peters,a Nicolai Burzlaff*,a

aInorganic Chemistry, Department of Chemistry and Pharmacy,

University of Erlangen-Nürnberg, Egerlandstraße 1, D-91058, Erlangen, Germany

Tripodal ligands such as bis(pyrazol-1-yl)acetic acid (Hbpza) and its derivatives (e. g.

Hbdmpza, Hbdtbpza) have shown to be versatile structural mimics for the facial 2-His-1-

carboxylate triad of non-heme iron oxygenases and for the 2-His-1-carboxylate motif of

gluzincines [1]. Recently, the work of our group and others has focused on the synthesis of

imidazole based tripodal ligands such as the bis(N-methylimidazol-2-yl)propionic acid

(Hbmip) [2,3]. Here, we report on the synthesis of bis(N-methylimidazol-2-ylmethyl)acetic

acid (Hbmima) as a first example of a new class of tridentate N,N,O ligands. Complexes

bearing this and related ligands as well as coordination polymers thereof will be presented.

CO2

N

NH N

NMe Me

Hbmima

N

N

N

N

Me

Me

Hbmip

CO2H

NNN N

CO2H

NNN N

Me

Me

Me

Me

CO2H

NNN N

tBu tBu

tButBu

Hbpza Hbdmpza Hbdtbpza

CO2H

[1] Beck, A.; Barth, A.; Hübner, E.; Burzlaff, N. Eur. J. Inorg. Chem. 2003, 42, 7182 – 7188. [2] Peters, L.; Hübner, E.; Burzlaff, N. Organomet. Chem. 2005, 690, 2009 – 2016. [3] Bruijnincx, C. P. A.; Lutz, M.; Spek, A. L.; Hagen, W. R.; Weckhuysen, B. M.; van Koten, G.; Klein Gebbink, R. J. M. J. Am. Chem. Soc. 2007, 8, 2275 – 2286.

10/4/2008 S51 9:55 – 10:10

Mononuclear Lanthanide and Titanium Imido Complexes

Alexandra Trambitas, Tarun K. Panda, Sören Randoll, Thomas Bannenberg, MatthiasTamm*

Institut für Anorganische und Analytische Chemie, Technische Universität Carolo-

Wilhelmina, Hagenring 30, D-38106, Braunschweig, Germany

In the last two decades transition metal imido complexes have attracted considerable

interest since they proved to be active catalysts in different catalytic transformations like

metathesis, cycloaddition, C-H activation, polymerisation and hydroamination reactions [1].

In stark contrast to the rich chemistry of imido complexes containing d-block elements,

lanthanide imido complexes are largely unexplored, and reports on well-defined imido

complexes containing 4f-elements are scarce [2].

IA

2

IBN

N

R

R

NN

N

R

R

N

Scheme 1

As a terminal ligand, the formally dianionic imido ligand (NR)2- coordinates with a metal-

nitrogen multiple bond consisting of one and either one or two interactions [3]. This

resembles the bonding in transition metal complexes containing monoanionic imidazolin-2-

iminato ligands of type I, which can be described by the two limiting resonance structures IA

and IB (Scheme 1), indicating that the ability of the imidazolium ring to stabilize a positive

charge leads to highly basic ligands with a strong electron donating capacity towards early

transition metals [3]. Therefore, lanthanide complexes with terminal imidazolin-2-iminato

ligands, [4] which will be presented here, can serve as accurate models for elusive

mononuclear lanthanide imido complexes, and their structural investigation could lead to a

better understanding of lanthanide-nitrogen multiple bonding [2]. Novel Ti imido complexes

have been also synthesised and their reactivity towards cyclooctatetraene studied.

[1] L. H. Gade and P. Mountford, Coord. Chem. Rev., 2001, 216–217, 65.

[2] T. R. Cundari, Chem. Rev., 2000, 100, 807.

[3] M. Tamm, D. Petrovic, S. Randoll, S. Beer, T. Bannenberg, P. G Jones, J. Grunenberg, Org. Biomol. Chem., 2007, 5, 523

[4] T. K. Panda, S. Randoll, C.G. Hrib, P. G. Jones, T. Bannenberg, M. Tamm, Chem. Comm., 2007, 47, 5007 and

unpublished results.

10/4/2008 S52 10:10 – 10:25

Synthesis and Structure of Tetrameric Gallium (I) Amides

Annekathrin Seifert,a Gerald Linti *,a

aUniversity of Heidelberg, Institute of Inorganic Chemistry, Im Neuenheimer Feld 270, 69120

Heidelberg, Germany

Gallium amides, with gallium in the low oxidation state +I, might be well-defined starting

materials for the synthesis of novel organo gallium compounds and metalloid gallium clusters

[1]. The cluster chemistry of gallium has made vast progress during the last years. In most

cases bulky organyl or silyl substituents have been used.

The amino substituted gallatetrahedranes Ga4[N(SiMe3)dipp]4 (dipp = 2,6

diisopropylphenyl), 1, and Ga4tmp4 (tmp = 2,2,6,6-tetramethylpiperidino), 2, are the first

oligomeric gallium(I)amides. Their synthesis [2], structure, bonding and some reactions of

these compounds will be discussed.

= tmp

NRR' =

4 "GaI" + 4 LiNRR' [GaNRR']4toluene/thf

-78°C-LiI(-Ga)

= N(SiMe3)dippN(SiMe3)

iPr

iPr

N=

1

2

ORTEP view of the molecule 2.

[1] Linti, G., Schnöckel, H., Uhl, W., Wiberg, N. in: Molecular Clusters of the Main Group

Elements (Eds.: Driess, M., Nöth, H.), Wiley-VCH, Weinheim, 2004, pp. 126-168.

[2] Seifert, A.; Linti, G., Eur. J. Inorg. Chem. 2007, 5080 – 5086.

10/4/2008 S53 10:25 – 10:40

Synthesis and structure of alkylaluminium and alkylgallium derivatives

of phthalic and phthalamic acid

Daniel Prochowicz,a Wojciech Bury,a Janusz Lewi ski a and Iwona Justyniak,b

aFaculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw bInstitute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52,

01-224, Warsaw, Poland

The chemistry of organoaluminum carboxylates and carboxylate alumoxanes has been

under investigation in the last few decades due to their wide potential applications in materials

science as precursors for alumina fibers or aluminum oxides. Nevertheless, the knowledge

about the structure and reactivity of organogallium carboxylates is rather scant. Recently, we

have reported the synthesis and structure characterization of the first examples of

alkylaluminum derivatives of mono- and dicarboxylic acids [1]. We have also provided an

efficient route to tetramethylalumoxane moieties and carboxylate-substituted alumoxanes [2].

Here we present the synthesis and structural characterization of a series of clusters derived

from Me3Ga and phthalic acid by using various molar ratios. Moreover, we have extended the

former studies to phthalamic acid (Scheme 1). Addition of 2 equiv. of Me3Al to phthalamic

acid resulted in the formation of the new tetranuclear adduct I. In contrast, the similar reaction

with Me3Ga at different molar ratios afforded the dinuclear gallium compound II and a novel

carboxylate galoxane III was obtained. The reactivity of novel aluminum and gallium

derivatives of phthalic and phthalamic acid will also be discussed.

COOH

CONH2

Al

O

NH

O

Al

Al

O

O

NH

O

Al

O

O

NH

GaO

GaGa

O

O

O

NHO

OGa

GaO

Ga

O

NH2

O

Ga

O

O

NH2

O

Ga

O

n Me3Ga

2 Me3Al

n = 1 i 2

2 Me3Ga

1h

1h

24h

I

II

III

Scheme 1

[1] J. Lewi ski, J. Zachara, I. Justyniak, Organometallics 16, 1997, 3859. J. Lewi ski, J. Zachara,

I. Justyniak, Inorg. Chem. 37, 1998, 2575.

[2] J. Lewi ski, W. Bury, I. Justyniak, J. Lipkowski, Angew. Chem. Int. Ed. 45, 2006, 2872

10/4/2008 S54 10:40 – 10:55

Cyclopentadienyl Iron - Bismuth Compounds

Synthesis, Structure and Reactivity

Katarzyna Wójcik, Petra Ecorcharda), Heinrich Langa), Michael Mehring *

Technische Universität Chemnitz, Institut für Chemie, 09107 Chemnitz, Germany. a) X-ray crystallography

Over the last years there has been considerable interest in bismuth compounds because of

their wide spectrum of applications in many aspects of our live. For example for more than

two centuries bismuth compounds have been used in medicine and still can be found in

medical formulations [1]. Recently, bismuth containing heterometallic oxides, thin films,

nanoparticles and nanofibers have received considerable interest for their potential

applications as oxidation catalysts, next generation memory devices, high Tc

superconductors, high temperature electrolytes, nonlinear optical materials and ‘‘green’’

lubricant [2, 3].

In our work we focus on heterometallic bismuth transition metal compounds [4, 5], which

are of interest as a new class of potential starting materials for more sophisticated molecular

precursors for heterometallic bismuth–containing compounds [5]. In this context the reactivity

of cyclopentadienyldicarbonyl iron derivatives with bismuth halides (Cl, Br), bismuth

siloxides and alkoxides have been studied. The synthesis, structure and reactivity of

[Cpy(CO)2Fe-BiX2] (Cpy- C5H5, tBu2-C5H3,C5Me5, X- Cl, Br) will be discussed.

Fig1.The solid state structure of [(C5H5)(CO)2Fe-BiBr2]

[1] N. Yang, H. Sun, Coord. Chem. Rev., 2007, 251, 2354 [2] M.C. Arbosa, J. Frejlich, Trends in Optics and Photonics, 2003, 87, 8731[3] O. Rohr, Ind. Lubr. Tribol., 2002, 54, 153 [4] T. Gröer, M. Scheer, J. Chem Soc., Dalton Trans., 2000, 647 [5] M. Mehring, Coord. Chem. Rev., 2007, 251, 974

Alphabetical Index of Lecturers

Bek, D. S9 Nerkowski, T. S23B aszczyk, I. S13 Peitz, S. S28Brückmann, N. E. S19 Pichlmaier, M. S43Deáky, V. S32 Prochowicz, D. S52Domínguez, I. S18 Rose, M. S4Döring, K. S7 Schirrmacher, C. S6Dostál, L. IL7 Schreiner, C. S25Dr g, A. S26 Schulz, J. S15Dudle, B. S38 Seifert, A. S51Dudziec, B. S40 Sienkiewicz, J. S8Dybov, A. S44 Simkowa, I. S48Eignerová, B. S10 Sobota, P. IL1Filimon, S. S46 Steinborn, D. IL2Fischer, N. S49 Št pni ka, P. IL6Frenking, G. IL5 Švec, P. S31Grzegorzek, N. S47 Szulmanowicz, M. S. S16Herbaczy ska, B. S36 Tagne Kuate, A. C. S30Huber, W. S21 Tauchman, J. S17Ionescu, C. S12 Trambitas, A. S50Ja yna, I. S37 Walkowiak, J. S41Jiang, Y. S39 Wójcik, K. S53Jipa, I. S3 Wrona, A. S20Kaczorowski, T. S5 Zakrzewski, J. KL2Kami ska, E. S35Kami ski, R. S45Kessler, F. S14Klahn, M. S27Kraszewska, I. S29Krauzy - Dziedzic, K. S24Lama , M. S22Linseis, M. A. S42Low, P. J. KL1Mansfeld, D. S1Marciniec, B. IL4Marczewski, M. S11Martincová, J. S33Meyer, F. IL3Meyer, M. S2Mucha, B. S34

Addresses

David Bek Research Group Prof. Dr. Ji í ejkaJ. Heyrovský Institute of Physical Chemistry AS CR, v.v.i, Dolejškova 3 182 23 Prague 8, Czech Republic [email protected]

Dr. Libor Dostál Department of General and Inorganic ChemistryFaculty of Chemical Technology University of Pardubice nám. s. Legií 532 10 Pardubice, Czech Republic [email protected]

Izabela B aszczykResearch Group Prof. Dr. Anna Trzeciak Faculty of Chemistry University of Wroc aw14 F. Joliot-Curie 50-383 Wroc aw, Poland [email protected]

Anna Dr gResearch Group Prof. Dr. Piotr Sobota Faculty of Chemistry Wroc aw University 14, F. Joliot-Curie 50-383 Wroc aw, Poland [email protected]

Nadine E. Brückmann Research Group Prof. Dr. Wolfgang Kläui Heinrich-Heine-Universtiy of Düsseldorf Universitätsstr. 1 40225 Düsseldorf, Germany [email protected]

Balz Dudle Research Group Prof. Dr. Heinz Berke Institut of inorganic chemistry University of Zürich Winterthurerstrasse 190 8057 Zürich, Switzerland [email protected]

Vajk Deáky Research Group Prof. Dr. Klaus Jurkschat Lehrstuhl für Anorganische Chemie II Technische Universität Dortmund D-44221 Dortmund, Germany [email protected]

Beata Dudziec Research Group Prof. Dr. Bogdan Marciniec Adam Mickiewicz University Faculty of Chemistry Department of Organometallic Chemistry Grunwaldzka 6 60-780 Pozna , Poland [email protected]

Katrin Döring Research Group Prof. Dr. Heinrich Lang Technische Universität Chemnitz Fakultät für Naturwissenschaften Institut für Chemie Lehrstuhl für Anorganische Chemie Straße der Nationen 62 09111 Chemnitz, Germany [email protected]

Alexander Dybov Research Group Prof. Dr. Heinz Berke Institut of inorganic chemistry University of Zürich Winterthurerstrasse 190 8057 Zürich, Switzerland [email protected]

Irene Domínguez Research Group Prof. Dr. Ji í ejkaJ.Heyrovský Institute of Physical Chemistry AS CR, v.v.i, Dolejškova 3 182 23 Prague 8, Czech Republic [email protected]

Barbara Eignerová Research Group Prof. Dr. Martin Kotora Department of Organic and Nuclear ChemistryFaculty of Science Charles University Hlavova 2030 12843 Prague 2, Czech Republic [email protected]

Sabina Filimon Research Group Prof. Dr. Matthias Tamm Institut für Anorganische und Analytische ChemieTechnische Universität Carolo-Wilhelmina zu Braunschweig Hagenring 30 38106 Braunschweig, Germany [email protected]

Cezar Ionescu Research Group Prof. Dr. Eckhard Dinjus ITC-CPVForschungszentrum Karlsruhe 76201 Karlsruhe, Germany [email protected]

Nina Fischer Research Group Prof. Dr. Nicolai Burzlaff Inorganic ChemistryDepartment of Chemistry and Pharmacy University of Erlangen-Nürnberg Egerlandstraße 1 D-91058 Erlangen, Germany [email protected]

Izabela Ja ynaResearch Group Prof. Dr. Piotr Sobota Faculty of Chemistry University of Wroc aw14, F. Joliot-Curie 50-383 Wroc aw, Poland [email protected]

Prof. Dr. Gernot Frenking Fachbereich Chemie Philipps-Universität Hans-Meerwein-Strasse D-35043 Marburg, Germany [email protected]

Yanfeng Jiang Research Group Prof. Dr. Heinz Berke Institut of Inorganic Chemistry University of Zürich Winterthurerstrasse 190 8057 Zürich, Switzerland [email protected]

Norbert Grzegorzek Research Group Prof. Dr. Lechos aw Latos-Gra y skiDepartment of Chemistry University of Wroc aw14 F. Joliot-Curie St/ Wroc aw 50-383, Poland [email protected]

Ilona JipaResearch Group Prof. Dr. Ulrich Zenneck Department für Chemie und Pharmazie Universität Erlangen-Nürnberg Egerlandstrasse 1 D-91058 Erlangen, Germany [email protected]

Beata Herbaczy skaResearch Group Prof. Dr. Antoni PietrzykowskiWarsaw University of Technology Faculty of Chemistry Koszykowa 75 00-662 Warsaw, Poland [email protected]

Tomazs Kaczorowski Research Group Prof. Dr. Janusz LipkowskiDepartment of Chemistry Warsaw University of Technology Noakowskiego 3 00-664 Warsaw, Poland [email protected]

Wilhelm Huber Research Group Prof. Dr. Wolfgang Kläui Heinrich-Heine-Universtiy of Düsseldorf Universitätsstr. 1 40225 Düsseldorf, Germany [email protected]

El bieta Kami skaResearch Group Prof. Dr. Antoni PietrzykowskiWarsaw University of Technology Faculty of Chemistry Noakowskiego 3 00-664 Warsaw, Poland [email protected]

Rados aw Kami skiResearch Group Prof. Dr. Krzysztof Wo niakWarsaw University of Technology Faculty of Chemistry Noakowskiego 3 00-664 Warsaw, Poland [email protected]

Michael A. Linseis Research Group Prof. Dr. Rainer F. Winter Institut für Anorganische Chemie Universität Regensburg Universitätsstraße 31 93053 Regensburg, Germany [email protected]

Florian Kessler Research Group Prof. Dr. Helmut Fischer University of Konstanz Universitätsstraße 10 78457 Konstanz, Germany [email protected]

Dr. Paul J. Low Department of Chemistry Durham University South Rd Durham, DH1 3LE [email protected]

Marcus Klahn Research Group Prof. Dr. Uwe Rosenthal Leibniz-Institut für Katalyse e. V. an der Universität Rostock Albert-Einstein-Str. 29a D-18059 Rostock, Germany [email protected]

Dirk Mansfeld Research Group Prof. Dr. Michael Mehring Technische Universität Chemnitz Institut für Chemie Koordinationschemie09107 Chemnitz, Germany [email protected]

Izabela Kraszewska Research Group Prof. Dr. Janusz Lewi skiWarsaw University of Technology Faculty of Chemistry Noakowskiego 3 00-664 Warsaw, Poland [email protected]

Prof. Dr. Bogdan Marciniec Department of Organometallic Chemistry Faculty of Chemistry Adam Mickiewicz University Grunwaldzka 6 60-780 Pozna , Poland [email protected]

Katarzyna Krauzy – Dziedzic Research Group Prof. Dr. Piotr Sobota Faculty of Chemistry University of Wroc aw14, F. Joliot-Curie 50-383 Wroc aw, Poland [email protected]

Maciej Marczewski Research Group Prof. Dr. Antoni PietrzykowskiWarsaw University of Technology Faculty of Chemistry Noakowskiego 3 00-664 Warsaw, Poland [email protected]

Martin LamaResearch Group Doc. RNDr. Petr Št pni kaCharles University in Prague Department of Inorganic Chemistry Hlavova 2030 128 40 Prague, Czech Republic [email protected]

Jana Martincová Research Group Prof. Dr. Klaus Jurkschat Lehrstuhl für Anorganische Chemie II Technischen Universität Dortmund D-44227 Dortmund, Germany [email protected]

Prof. Dr. Franc Meyer Institut für Anorganische Chemie Georg-August-Universität Göttingen Tammannstrasse 4 D-37077 Göttingen, Germany [email protected]

Daniel Prochowicz Research Group Prof. Dr. Janusz Lewi skiWarsaw University of Technology Faculty of Chemistry Noakowskiego 3 00-664 Warsaw, Poland [email protected]

Mareike Meyer Research Group Prof. Dr. Wolfgang Kläui Heinrich-Heine-Universtiy of Düsseldorf Universitätsstr. 1 40225 Düsseldorf, Germany [email protected]

Marcus Rose Research Group Prof. Dr. Stefan Kaskel Department of Inorganic Chemistry Dresden University of Technology Mommsenstr. 6 01062 Dresden, Germany [email protected]

Bartosz Mucha Prof. Dr. Janusz Zakrzewski Department of Chemistry University of ód90-136 ódNarutowicza 68, Poland [email protected]

Christian Schirrmacher Research Group Prof. Dr. Siemeling Universität Kassel Heinrich-Plett-Str. 40 34132 Kassel, Germany [email protected]

Tomasz Nerkowski Research Group Prof. Dr. Piotr Sobota Faculty of Chemistry University of Wroc aw14, F. Joliot-Curie 50-383 Wroc aw, Poland [email protected]

Claus Schreiner Research Group Prof. Dr. Heinrich Lang Technische Universität Chemnitz Institut für Chemie Lehrstuhl für Anorganische Chemie Straße der Nationen 62 09111 Chemnitz, Germany [email protected]

Stephan Peitz Research Group Prof. Dr. Uwe Rosenthal Leibniz-Institut für Katalyse e. V. an der Universität Rostock Albert-Einstein-Str. 29a D-18059 Rostock, Germany [email protected]

Ji í Schulz Research Group Doc. RNDr. Petr Št pni kaDepartment of Inorganic Chemistry, Faculty of Science, Charles University, Hlavova 2030, 12840 Prague, Czech Republic; E-mail:[email protected], [email protected]

Markus Pichlmaier Research Group Prof. Dr. Rainer F. Winter Institut für Anorganische Chemie Universität Regensburg Universitätsstraße 31 93040 Regensburg, Germany [email protected]

Annekathrin Seifert Research Group Prof. Dr. Gerald Linti University of Heidelberg Institute of Inorganic Chemistry Im Neuenheimer Feld 270 69120 Heidelberg, [email protected]

Justyna Sienkiewicz Research Group Prof. Dr. Zofia Rz czy skaDepartment of General and Coordination ChemistryFaculty of Chemistry Maria Curie-Sk odowska University 20-031 Lublin, Poland [email protected]

Michal S. Szulmanowicz Research Group Prof. Dr. Anna M. Trzeciak Faculty of Chemistry University of Wroc aw14 F.Joliot-Curie 50-383 Wroc aw, Poland [email protected]

Irena Simkowa Research Group Prof. Dr. Lechos aw Latos-Gra y skiDepartment of Chemistry University of Wroc aw14 F. Joliot-Curie St. 50-383 Wroc aw, Poland [email protected]

Alain Charly Tagne Kuate Research Group Prof. Dr. Klaus Jurkschat Lehrstuhl für Anorganische Chemie II Technische Universität Dortmund D-44221 Dortmund, Germany [email protected]

Prof. Dr. Piotr Sobota Faculty of Chemistry Wroc aw University 14, F. Joliot-Curie 50-383 Wroc aw, Poland [email protected]

Ji í Tauchman Research Group Doc. RNDr. Petr Št pni kaCharles University in Prague Faculty of Science Department of Inorganic hemistry Hlavova 2030 128 40 Prague, Czech Republic [email protected]

Prof. Dr. Dirk Steinborn Institut für Chemie – Anorganische Chemie Martin-Luther-Universität Halle-Wittenberg Kurt-Mothes-Straße 2 06120 Halle, Germany [email protected]

Alexandra Trambitas Research Group Prof. Dr. Matthias Tamm Institut für Anorganische und Analytische ChemieTechnische Universität Carolo- Wilhelmina zu Braunschweig Hagenring 30 38106 Braunschweig, Germany [email protected]

Doc. RNDr. Petr Št pni kaCharles University in Prague Faculty of Science Department of Inorganic Chemistry Hlavova 2030 128 40 Prague, Czech Republic [email protected]

J drzej Walkowiak Research Group Prof. Dr. Bogdan Marciniec Department of Organometallic Chemistry Adam Mickiewicz University Grunwaldzka 6 60-780 Pozna , Poland [email protected], [email protected]

Petr ŠvecResearch Group Prof. Dr. Aleš R ži kaDepartment of General and Inorganic ChemistryFaculty of Chemical Technology University of Pardubice nám. s. legií 565, CZ-532 10, Pardubice, Czech Republic [email protected]

Katarzyna Wójcik Research Group Prof. Dr. Michael Mehring Technische Universität Chemnitz Institut für Chemie Koordinationschemie09107 Chemnitz, Germany [email protected]

Anna Wrona Research Group Prof. Dr. Janusz ZakrzewskiDepartment of Organic Chemistry University of ódNarutowicza 68 90-136 ód , Poland [email protected]

Prof. Dr. Janusz Zakrzewski Department of Organic Chemistry University of ódNarutowicza 68 90-136 ód , Poland [email protected]

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th International Seminar for Ph. D. Students on ... · Welcome Address A very warm welcome is...

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Transcript of th International Seminar for Ph. D. Students on ... · Welcome Address A very warm welcome is...