Die Freiheit der Meinung setzt voraus, dass man eine hat. Heinrich Heine ( )

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1 Scientific Programm

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3 Die Freiheit der Meinung setzt voraus, dass man eine hat. Heinrich Heine ( )

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5 Table of Contents Conference Programm 1 Abstracts of ral Presentations 4 Abstracts of Poster Presentations 29 List of Participants 58 Public transport Informations 62

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7 Monday, :00-14:50: IL01 Prof. Dr. Matthias Tamm (TU Braunschweig) Synthesis and eactivity of Functionalized Cycloheptatrienyl-Cyclopentadienyl Sandwich Complexes 14:50-15:15 P01 Matthias Kanthak (uhr-universität Bochum) Chelated uthenium Complexes of Functionalized Pentaarylcyclopentadienes 15:15-15:40 P02 Katharina Weitershaus (uprecht-karls-universität Heidelberg) Halfsandwich Titanium Complexes supported by 2-Aminopyrroline Ligands --- Coffee Break :15-16:40 P03 Manuela Gross (Julius-Maximilians-Universität Würzburg) Synthesis, Structure, and eactivity of Disila[2]metallocenophanes 16:40-17:05 P04 Daniel Weismann (TU Kaiserslautern) Substituted cyclopentadienyl and hexadienyl ligands in BiPh 3 -based TLE-reactions 17:05-17:30 P05 Thomas Glöge (TU Braunschweig) uthenium halfsandwich complexes with superbasic diimine ligands 17:30-18:30 eception/postersession Evening eception 1

8 Tuesday, :00-9:50 IL02 Prof. Dr. Didier Astruc (Université Bordeaux I) rrocene in nanosciences 9:50-10:15 P06 Daniel Franz (Johann-Wolfgang-Goethe-Universität Frankfurt) Synthesis of π-conjugated boron-containing polymers 10:15-10:40 P07 Barbara Enk (Universität Innsbruck) ew imino-functionalized fulvenes: versatile ambidentate ligands for novel ruthenocene complexes and olefin polymerization precatalysts --- Coffee Break :15-11:40 P08 Dr. Christian Färber (Universität Kassel) A stable crystalline -heterocyclic carbene with a 1,1 -ferrocenediyl backbone 11:40-12:05 P09 Markus Graser (Universität Innsbruck) Bis(imino) remote -heterocyclic carbene complexes 12:05-12:30 P10 Jiří Tauchman (Charles-University Prague) Phosphanylferrocene Conjugates with Amino Acids --- Lunch Break :00-14:50: IL03 Prof. Dr. Karl Kirchner (TU Wien) Transition Metal Pincer Complexes based on Aminophosphines Synthesis and Applications 14:50-15:15 P11 Tomáš Bobula (Charles-University Prague) Mo-Catalyzed Cross-Metathesis eaction of Propynylferrocene 15:15-15:40 P12 adine Langenscheidt-Dabringhausen (WTH Aachen) pen uthenocene: Just Another uthenium Precursor? --- Coffee Break :15-16:40 P13 Bram Pluijmaekers (heinische Friedrichs-Wilhelms-Universität Bonn) Dimerisation of bis(dimethylamino)acetylene on i(0) centers 16:40-17:05 P14 Dieter Schaarschmidt (TU Chemnitz) A Convenient Way to Functionalized Phosphinoferrocenes 17:05-17:30 P15 Wolfgang Bulla/ Dr. Hubert Jungbluth (Innospec Herne) 17:30-18:30 Postersession PLUTcen Industrial Production and Applications as Fuel Additive Evening Conference-Dinner 2

9 Wednesday, :00-9:50 IL04 Prof. Dr. Holger Butenschön (Leibniz-Universität Hannover) rrocene - A 3D Benzene 9:50-10:15 P16 Frank Pammer (TU Kaiserslautern) Dibenzo[c,g]fluorene: exploring the concept of aromaticity on complexes of an intrinsically chiral Cp-ligand 10:15-10:40 P17 Jessica Lemke (uhr-universität Bochum) Synthesis of ruthenium and rhodium imidazolium peptide conjugates --- Coffee Break :15-11:40 P18 Dr. Monika eger (Universität Stuttgart) emarkable Binding Capacity of [(dppf)cu] + for Weakly Coordinating π-acceptor Chelate Ligand 11:40-12:05 P19 Daniel ebler (Johannes-Gutenberg-Universität Mainz) ptical Detection of Anions and Small Biomolecules with rrocene Derivatives 12:05-12:30 P20 S. David Köster (uhr-universität Bochum) rrocene-peptide and -PA Bioconjugates via Click Chemistry 3

10 ral Contributions: IL P Invited Lectures ral Presentations IL01 Prof. Dr. Matthias Tamm (TU Braunschweig) P01 Matthias Kanthak (uhr-universität Bochum) P02 Katharina Weitershaus (uprecht-karls-universität Heidelberg) P03 Manuela Gross (Julius-Maximilians-Universität Würzburg) P04 Daniel Weismann (TU Kaiserslautern) P05 Thomas Glöge (TU Braunschweig) IL02 Prof. Dr. Didier Astruc (Université Bordeaux I) P06 Daniel Franz (Johann-Wolfgang-Goethe-Universität Frankfurt) P07 Barbara Enk (Universität Innsbruck) P08 Dr. Christian Färber (Universität Kassel) P09 Markus Graser (Universität Innsbruck) P10 Jiří Tauchman (Charles-University Prague) IL03 Prof. Dr. Karl Kirchner (TU Wien) P11 Tomáš Bobula (Charles-University Prague) P12 adine Langenscheidt-Dabringhausen (WTH Aachen) P13 Bram Pluijmaekers (heinische Friedrichs-Wilhelms-Universität Bonn) P14 Dieter Schaarschmidt (TU Chemnitz) P15 Wolfgang Bulla/ Dr. Hubert Jungbluth (Innospec Herne) IL04 Prof. Dr. Holger Butenschön (Leibniz-Universität Hannover) P16 Frank Pammer (TU Kaiserslautern) P17 Jessica Lemke (uhr-universität Bochum) P18 Dr. Monika eger (Universität Stuttgart) P19 Daniel ebler (Johannes-Gutenberg-Universität Mainz) P20 S. David Köster (uhr-universität Bochum) 4

11 Synthesis and eactivity of Functionalized Cycloheptatrienyl- Cyclopentadienyl Sandwich Complexes Matthias Tamm Institut für Anorganische und Analytische Chemie, Technische Universität Carolo-Wilhelmina, Hagenring 30, Braunschweig, Germany. In recent years, my group has been involved in the synthesis and reactivity of highly strained ansa-cht-cp complexes of type I, 1 which have been shown to be susceptible to strain release by undergoing ring-opening polymerization reactions (Figure 1). In addition, the bending of the two rings in these 16-electron complexes opens a potential vacancy at the titanium centre, which thereby becomes accessible to monodentate ligands such as C or isocyanides. 2 In contrast, the formation of thermally labile isocyanide, carbene and phosphine adducts can be observed for the zirconium and hafnium complexes II without resorting to the introduction of a bridging unit. 3 This reactivity prompted us to synthesize phosphorous-functionalized zirconium and hafnium Cht-Cp complexes of type III, since these systems can be expected to develop interesting secondary interactions involving the Zr or Hf metal atoms. 4 The resulting metallo-supramolecular chemistry will be the main focus of this presentation. Me Me Ti E P Me 2 E Ti +L -L Me 2 E Ti L n E =, Ge I L = C, C, P 3 M P 2 M = Zr, Hf M +L -L M L III II Figure 1. Cycloheptatrienyl-cyclopentadienyl group 4 complexes. eferences 1. M. Tamm, Chem. Commun. 2008, (a) M. Tamm, A. Kunst, T. Bannenberg, E. Herdtweck, P. rsch, C. J. Elsevier, J. M. Ernsting, Angew. Chem. Int. Ed. 2004, 43, (b) M. Tamm, A. Kunst, E. Herdtweck, Chem. Commun. 2005, (c) M. Tamm, A. Kunst, T. Bannenberg, S. andoll, P. G. Jones, rganometallics 2007, 26, (a) M. Tamm, A. Kunst, T. Bannenberg, E. Herdtweck,. Schmid, rganometallics 2005, 24, (b). J. Baker, T. Bannenberg, A. Kunst, S. andoll, M. Tamm, Inorg. Chim. Acta 2006, 359, S. Büschel, A.-K. Jungton, T. Bannenberg, S. andoll, C. G. Hrib, P. G. Jones, M. Tamm, Chem. Eur. J. 2009, in press. 5

12 Chelated uthenium Complexes of Functionalized Pentaarylcyclopentadienes M. Kanthak, a A. Aniol, a I. M. ppel, b G. Dyker* a a uhr-universität Bochum, Faculty of Chemistry and Biochemistry, rganic Chemistry II, Universitätsstr. 150, Bochum, Germany. b uhr-universität Bochum, Faculty of Chemistry and Biochemistry, Analytical Chemistry, Universitätsstr. 150, Bochum, matthias.kanthak@rub.de Although the synthesis of cyclopentadienyl complexes with pendant donor groups has been a well established research field, 1 corresponding compounds with pentaphenylated cyclopentadienes are unknown. We have synthesized water- and air-stable ruthenium complexes with various chelating pentaarylcyclopentadiene ligands. Figure 1: Synthesis of ruthenium complexes 3, a,a : 1. u 3 (C) 12, 2. CHCl 3, b: hν The pendant coordination site is located at the ortho-position of one phenyl group. In general, the reaction 2 of the cyclopentadiene 1 with u 3 (C) 12 and chloroform (Figure 1) directly results in chelated complexes 3. Alternatively, irradiation of monodentate complex 2 leads to decarbonylation followed by an intramolecular coordination of the pendant group. The coordination establishes the ruthenium atom as a stable center of chirality. Most interestingly, only one possible diastereomer is detected for 3c and 3d, if the pendant donor is an enantiopure oxazoline. We are currently investigating scopes and limitations of enantioselective catalysis with these chiral ruthenium complexes. eferences 1. (a) U. emeling, Chem. ev. 2000, 100, (b) H. Butenschön, Chem. ev. 2000, 100, (c) P. Jutzi, T. edeker, Eur. J. Inorg. Chem. 1998, B. Martín-Matute, M. Edin, K Bogár, F. B. Kaynak, J.-E. Bäckvall, J. Am. Chem. Soc. 2005, 127,

13 Halfsandwich Titanium Complexes supported by 2-Aminopyrroline Ligands Katharina Weitershaus, a Hubert Wadepohl, a and Lutz H. Gade* a a Anorganisch-Chemisches Institut, Universität Heidelberg, Im euenheimer ld 270, Heidelberg, Germany lutz.gade@uni-hd.de Transition metal hydrazinediido compounds are of considerable interest with regard to the biological and synthetic fixation of molecular nitrogen. 1 ur investigations have focused on hydrazinediido complexes of group 4 elements whose chemistry is underdeveloped at this stage. n the other hand the chemistry of related imido compounds towards unsaturated molecules and their applications in hydroamination catalysis is well established. The work of our group 2 and others 3 has shown that group 4 complexes are on the one hand capable of - bond cleavage and on the other hand have the ability to perform [2+2] cycloaddition reactions. In 2002 dom reported the use of terminal hydrazinediido complexes in catalytic hydrohyrazination 4 and iminohydrazination 5 reactions of alkynes. The isolation of catalytic intermediates and the predictability of the behavior of hydrazinediido ligands towards unsaturated molecules remain elusive. In order to achieve this objective, it is important to further our knowledge on the reactivity of hydrazinediido compounds. A series of halfsandwich titanium hydrazinediido complexes, supported by 2-aminopyrroline ligands, 6 have been synthesised and characterised. The complexes were prepared by imido exchange reaction 7 from the corresponding imido complexes reported previously. Their behaviour towards unsaturated molecules such as thiocyanates, isothiocyanates, azides, alkynes and allenes was studied in stoichiometric reactions and the products were characterised spectroscopically and by X-ray diffraction. Furthermore we also tested our hydrazinediido complexes in catalytic hydrohydrazination reactions of terminal alkynes where a high selectivity towards the Markovnikoff product and a considerable reactivity even at room temperature was observed. eferences 1... Schrock, Acc. Chem. es., 2005, 38, H. Herrmann, J. Llorett, H. Waddepohl, L. H. Gade, Angew. Chem. Int. Ed., 2007, 46, P. J. Walsh, M. J. Carney,. G. Bergman, JACS, 1991, 113, 6343; J. D. Selby, C. D. Manley, M. liz, A. D. Schwarz, E. Clot, P. Mountford, Chem Commun, 2007, C. Cao, Y. Shi, A. L. dom, rg. Lett., 2002, 4, s. Banerjee, Y. Shi, C. Cao, A. L. dom, J rganomet. Chem., 2005, 690, 5066; S. Banerjee, A. L. dom, rganometallics, 2006, 25, B. D. Ward, H. isler, K. Weitershaus, S- Bellemin-Laponnaz, H. Wadepohl, L. H. Gade, Inorg. Chem., 2006, 45, A. J. Blake, P. E. Collier, S. C. Dunn, W.-S. Li, P. Mountford,. V. Shishikin, J. Chem. Soc, Dalton Trans., 1997,

14 Synthesis, Structure, and eactivity of Disila[2]metallocenophanes M. Gross, K. adacki, and H. Braunschweig* Julius-Maximilians-Universität Würzburg, Faculty of Chemistry and Pharmacy, Department of Inorganic Chemistry, Am Hubland, 97074, Würzburg, Germany. Disila[2]metallocenophanes of groups 4 and 8 are already known and their reactivity has been thoroughly investigated. We, however, succeeded in the preparation of some new disila-brigded ansa-complexes by lithiation of 1,2-bis(cyclopentadienyl)-1,1,2,2-tetramethyldisilane and subsequent reaction with suitable metalhalides. 1 Me Me Me Me 1) 2 BuLi 2) x Me Me Me Me ML n x = MoCl 5 / a[bh 4 ] [WCl 4 (dme)] / Li[AlH 4 ] [CoBr 2 (dme)] [icl 2 (dme)] ML n = MoH 2 WH 2 Co i + Isomere f particular interest is the reactivity of the E E-bond of [2]metallocenophanes (E = B, ). Some homogenous and heterogenous catalyzed insertions of unsaturated organic substrates as well as oxidative addition to late transition metals have been reported. 2 ecently, we accomplished for the first time an intramolecular reaction under cleavage of the -bond. The ansa-molybdenocenedihydride reacts photochemically under elimination of hydrogen resulting in a twofold bridged disila[1],[1]molybdenocenophane. Furthermore, the synthesized ansa-complexes reveal a manifold and unexpected reactivity. Me Me Me Me Mo H H hν -H 2 Me Me Me Me Mo Me Me Me Me Mo eferences 1. (a) H. Braunschweig, M. Gross, K. adacki, rganometallics 2007, 26, (b) H. Braunschweig, F. Breher, M. Kaupp, M. Gross, T. Kupfer, D. ied, K. adacki, S. Schinzel, rganometallics 2008, 27, (c) H. Braunschweig, M. Gross, K. adacki, Angew. Chem. Int. Ed. 2008, 47, (a) H. Braunschweig, T. Kupfer, M. Lutz, K. adacki, F. Seeler,. gritz, Angew. Chem. Int. Ed. 2006, 45, (b) H. Braunschweig, T. Kupfer, rganometallics 2007, 26, (c) H. Braunschweig, T. Kupfer, J. Am. Chem. Soc. 2008, 130, (d) H. Braunschweig, M. Kaupp, C. J. Adams, T. Kupfer, K. adacki, S. Schinzel, J. Am. Chem. Soc. 2008, 130,

15 Substituted cyclopentadienyl and hexadienyl ligands in BiPh 3 -based TLE-reactions D. Weismann, 1,2 A. Verma, 1 M. Gillett-Kunnath, 1 G. B. Deacon, 3 H. tzmann, 2 K. uhlandt-senge 1 1 Dept. of Chemistry, CST 1-014, Stracuse, Y Fachbereich Chemie, TU Kaiserslautern, Germany 3 School of Chemistry, Monash University, Clayton, 3800 Australia Based on our recent work on using edox Transmetallation/ Ligand Exchange (TLE) using BiPh 3 for the synthesis of alkaline earth metal amides 1, we here demonstrate the potential of TLE for the synthesis of organoalkaline earth complexes. By employing cyclopentadiene ligands displaying different degrees of steric bulk in addition to several related ligand systems we demonstrate the influence of ligand size in the preparation of the target compounds. We will also discuss the preparation of alkaline earth metal hexadienyl complexes by employing similar methodology. 1) Gillett-Kunnath, M. M., MacLellan, J. G., Forsyth, C. M., Andrews, P. C., Deacon, G. B., uhlandt-senge, K. BiPh 3 A convenient synthon for heavy alkaline earth metal amides. Chem. Commun. 2008, Advance article on the web B806948D. 9

16 uthenium halfsandwich complexes with superbasic diimine ligands T. Glöge, Dejan Petrovic, and M. Tamm* a a Technische Universität Braunschweig,Fakultät für Lebenswissenschaften, Institut für Anorganische und Analytische Chemie, Hagenring 30, 38106, Braunschweig, Germany. t.gloege@tu-bs.de The chemistry of imidazolin-2-iminato ligands has been well established in important areas as alkyne metathesis 1 or olefin polymerisation 2. The coupling of two iminato moieties via an ethane-bridge leads to neutral, though very electron rich diimine ligands 3. They can donate between four and eight electrons depending on the electron demand of the coordinated metal fragment (compare structures 1a and 1b). 1a 1b Figure 1. Diimine ligand ( = Me, ipr). Three ruthenium halfsandwich moieties have been used to exemplify the characteristics of this ligand type. Figure 2 shows two arbitrary examples from this class of compounds with pseudo-trigonal or piano-stool coordination at the ruthenium centre. The ruthenium-nitrogen bond lengths are around 2.0Å long and therefore very short for neutral nitrogen donor atoms. Me Me Me u Me Cl Me u Cl 2 3 Figure 2. uthenium diimine complexes ( = Me, ipr). Cl These complexes have been studied concerning the addition of C or isocyanide ligands to provide further information about their activity 4. The ruthenium compounds have been shown to be catalytically active in direct hydrogenation and reductive transfer hydrogenation of carbonyl compounds. 1. M. Tamm, S. Beer, C. G. Hrib, P. G. Jones, K. Brandhorst, J. Grunenberg, Angew. Chem. Int. Ed. 2007, 46, M. Tamm, S. andoll, E. Herdtweck,. Kleigrewe, G. Kehr, G. Erker, B. ieger, Dalton Trans. 2006, milar ligands:. Kuhn, et.al. Z. aturforsch. 1998, 53, 997; G. Henkel, et. al., Eur. J. rg. Chem. 2005, 4879; 3. M. Tamm, D. Petrovic, T. Bannenberg, S. andoll, P. G. Jones, Dalton Trans. 2007, M. Tamm, D. Petrovic, T. Glöge, T. Bannenberg, C. G. Hrib, S. andoll, P. G. Jones, Eur. J. Inorg. Chem. 2007,

17 rrocene in nanosciences Didier Astruc, ISM, Université Bordeaux 1, Talence Cedex,, France In this lecture, the assembly of dendrimers and nanoparticles of various sizes and generations containing ferrocenyl termini will be illustrated. Supramolecular and nanoscience aspects involve redox functions 1 leading to applications in redox catalysis, 2 molecular recognition and electrochemical sensing (Figure 1). 3 S S S S S S S S S S S S S S S S S S S S ATP Sensing H 2 P P P CH 2 H H H H Figure 1. Au-nanoparticle-centered ferrocenyl dendrimer that senses ATP eferences 1. (a) C. rnelas, C. Belin, J. uiz, D. Astruc, J. Am. Chem. Soc. 2009, 11, DI: / ja ; (b) D. Astruc, C. rnelas, J. uiz, Acc. Chem. es. 2008, 41 (7) D. Astruc, rganometallic Chemistry and Catalysis, Springer, Heidelberg, 2007, Ch (a) M.-C. Daniel, J. uiz, D. Astruc, J. Am. Chem. Soc., 2003, 125, ; (b) M.-C. Daniel, J. uiz, S. late, J.-C. Blais, D. Astruc, J. Am. Chem. Soc., 2003, 125,

18 Synthesis of π-conjugated boron-containing polymers D. Franz a, U. D. Eckensberger a, A. Lorbach a, M. Scheibitz b, M. Wagner a a Goethe-Universität Frankfurt, Faculty of Chemistry, Department of Inorganic and Analytical Chemistry, Max-von-Laue-Straße 7, 60438, Frankfurt, Germany. b Former group member, now BASF AG. ur group spends effort on the synthesis of arylhydroboranes and arylbromoboranes with one or several boron moieties as precursors for boron-containing polymers. This led to the discovery of the condensation reaction of ferrocenylboranes by liberation of B 2 H 6 (borane coupling). 1 After abstraction of a hydride ion from lithium ferrocenyltrihydroborate the formed ferrocenylborane undergoes borane coupling to Fc 2 BH if not trapped as stable Lewis acidbase adduct. 2a Extension of this reactivity to the ditopic ferrocenylborane 1,1 -fc(bh 2 SMe 2 ) 2 yielded the corresponding polyferrocenylborane (compare Figure 1 A). 2a,2b 9,10-dihydro-9,10-diboraanthracene (DBA), which cannot liberate diborane by the condensation reaction pathway, was successfully applied in the hydroboration polymerization with diynes (Figure 1 B). 3a,3b The reaction of aryldibromoboranes with triethylsilane in the absence of an electron donor yielded the corresponding diarylbromoboranes accompanied by the liberation of B 2 H 6 and the formation of triethylbromosilane. 4a This reaction principle of hydrosilane-mediated coupling between arylbromoboranes was transferred to the dinuclear arylbromoboranes containing two boron moieties and the corresponding polyarylbromoboranes were obtained. 4b A n H 2 B Ar BH Ar 2 - n/2 B 2 H 6 B H n B n H B B H n Ar B B Ar n Figure 1: Polymerization reactions of dinuclear arylboranes. A: borane coupling (Ar = fc, ph), B: Hydroboration polymerization of 9,10-dihydro-9,10-diboraanthracene. eferences: 1. J. B. Heilmann, M. Scheibitz, Y. Qin, A. Sundararaman, F. Jäkle, M. Bolte, H.-W- Lerner, M. C. Holthausen, M. Wagner, Angew. Chem. Int. Ed. 2006, 45, (a) M. Scheibitz, J. W. Bats, M. Bolte, H.-W. Lerner, M. Wagner, rganometallics 2004, 23, (b) M. Scheibitz, Dissertation JWG Universität Frankfurt (a) A. Lorbach, Diploma Thesis Goethe-Universität Frankfurt (b) M. Wagner et al, paper in preparation 4. (a) U. D. Eckensberger, Diploma Thesis JWG Universität Frankfurt 2006 (b) M. Wagner et al, paper in preparation 12

19 ew imino-functionalized fulvenes: versatile ambidentate ligands for novel ruthenocene complexes and olefin polymerization precatalysts B. Enk, a H. Kopacka, a K. Wurst, a T. Müller, b and B. Bildstein* a a University of Innsbruck, Faculty of Chemistry and Pharmacy; Institute of General, Inorganic and Theoretical Chemistry; Innrain 52a, A-6020 Innsbruck, Austria. b University of Innsbruck, Faculty of Chemistry and Pharmacy; Institute of rganic Chemistry; Innrain 52a, A-6020 Innsbruck, Austria. barbara.enk@uibk.ac.at In general, in organometallic and coordination chemistry the reactivity and catalytic applications of metal complexes are controlled by the stereoelectronic properties of the ligand sphere. In this contribution, we present new [,]/[,]/Cp ligand families based on novel imino-functionalized fulvenes and their coordination chemistry: synthesis: modular, 1- or 2-step, starting from easily available synthons; structure: planar, conjugated, tautomeric, with tunable steric shielding and Lewis-basicity; variability: homo- or heteroleptic [,]/[,] chelate ligand systems with 1,2- or 1,3- substitution pattern and/or 1,2- or 1,3-functionalized cyclopentadienide precursors; reactivity: ambidentate ligands depending on the hard/soft character of the metal fragments: anionic ligands for κ 2 -[,]/[,]-7-ring metal chelates, neutral/anionic 1,2-/1,3-substituted (planar-chiral) ruthenocene-[,]/[,]-ligands; catalytic applications: new ligand families for olefin polymerization precatalysts of early to late transition metals. 13

20 A stable crystalline -heterocyclic carbene with a 1,1 -ferrocenediyl backbone C. Färber, a C. Bruhn, b and U. emeling* c a University of Kassel, Department of Chemistry, Heinrich-Plett-Staße 40, 34132, Kassel, Germany. b University of Kassel, Department of Chemistry, Heinrich-Plett-Straße, 34132, Kassel, Germany. c University of Kassel, Department of Chemistry, Heinrich-Plett-Straße 40, 34132, Kassel, Germany. faerber@uni-kassel.de -heterocyclic carbenes (HCs) are exceptionally important and versatile ligands suitable for a wide range of applications. 1 Even for the most widely investigated HCs (i. e. those containing a 5-membered ring system with no further heteroatoms), the electronic properties are still not fully understood. This is even more the case for HCs ring sizes other than 5 and/or heteroatoms in the backbone. 2 C Figure 1. x-membered HC with a 1,1 -ferrocenediyl backbone We are interested in HCs which contain a 1,1 -ferrocenediyl backbone, which would render this system redox-active (figure 1). We envisage that such HCs would be particularly suitable for investigations which use electrochemical methods to probe and switch the electronic properties of these ligands. First examples of metal complexes containing such HCs were published previously by Bielawski. 3 C h Cl C Mo C C C Figure 2. Free carbene 1 and its metal complexes 2 and 3 We present the synthesis of a new stable 2-adamantyl substituted carbene 1 with a redoxactive ferrocene-based backbone. It was characterised by X-ray crystallography. The carbene was utilised as a ligand in preparation of expected and unexpected metal complexes 2 and 3 (figure 2). 4 Support of this work by the Deutsche Forschungsgemeinschaft is gratefully acknowledged. eferences 1. S. P. olan (ed.), -Heterocyclic Carbenes in Synthesis, Wiley-VCH, Weinheim, See, for example: C. C. Scarborough, M. J. W. Grady, I. A. Guzei, B. A. Gandhi, E. E. Bunel, S. S. Stahl, Angew. Chem. Int. Ed. 2005, 44, D. M. Khramov, E. L. osen, V. M. Lynch, C. W. Bielawski, Angew. Chem., Int. Ed., 2008, 47, U. emeling, C. Bruhn, C. Färber, Chem. Commun., 2009, 98 14

21 Bis(imino) remote -heterocyclic carbene complexes M. Graser, a A. Solchinger, a H. Kopacka, a K. Wurst, a T. Müller, b and B. Bildstein* a a University of Innsbruck, Faculty of Chemistry and Pharmacy; Institute of General, Inorganic and Theoretical Chemistry; Innrain 52a, A-6020 Innsbruck, Austria. b University of Innsbruck, Faculty of Chemistry and Pharmacy; Institute of rganic Chemistry; Innrain 52a, A-6020 Innsbruck, Austria. markus.graser@uibk.ac.at During the past ten years -heterocyclic carbenes (HCs) have been very successfully implemented as novel steering ligands in catalytically active metal complexes, most notably for olefin metathesis and carbon-carbon cross-coupling reactions. In general, almost all of these ligand frameworks are based on imidazole or other azole heterocyclic cores where the carbene carbon is located in the "normal" position between the two nitrogen atoms. In contrast, "abnormal" HCs with the carbene carbon in a remote position, so-called "rhcs", are much less known. In this contribution, we report on new tridentate bis(imino)pyridylidene rhcs as new ligands of late transition metal centers for potential applications in homogenous and/or heterogenous catalysis, e.g. olefin polymerization. Conceptually, these tridentate [,C,] ligand systems were designed in close electronic and steric analogy to Brookhart/Gibson's very successful bis(imino)pyridine [,,]Cl 2 olefin polymerization catalysts. Synthetically, the key precursors of bis(imino)pyridylidene rhcs are accessible by a modular protocol, thereby allowing convenient steric modulation of the peripheral -aryl substituents. More demanding but nevertheless manageable is the formation of the "free" rhcs from their conjugated acids by interaction with suitable bases. Finally, transmetalation and/or complex formation with various transition metal halides gives access to [,C,] complexes. Spectroscopic results and single crystal X-ray structures as well as potential catalytic applications will be presented and discussed. 15

22 Phosphanylferrocene Conjugates with Amino Acids J. Tauchman, a and P. Štěpnička* a a Charles University in Prague, Faculty of Science, Department of Inorganic Chemistry, Hlavova 2030, , Prague, Czech epublic. tauchman@natur.cuni.cz In recent years, tremendous progress has been made in the design of new chiral ligands with phosphanylferrocene unit for the development of highly efficient metal-catalyzed asymmetric transformations. 1 We have recently reported the utilisation of several (phosphanyl)ferrocenecarboxylic acids and related amides combining planar and central chirality as ligands in enantioselective palladium-catalysed allylic alkylation reaction. 2,3 With this contribution, we report on the synthesis of new chiral phosphanylferrocene amides possessing amino acid pendant groups (types 1 and 2 in Figure 1). PPh2 C 2 H PPh2 PPh2 C 2 H C 2 H Hdpf (Sp)-HL (p)-hl H C PPh2 C H C Me C PPh2 Me PPh2 C H C Me 1 = ()-Me, (S)-Me, ()-CHMe2, (S)-CHMe2, ()-CH2Ph, (S)-CH2Ph 2 = H, ( )-Me, (S)-Me, ()-CHMe2, (S)-CHMe2, ()-CH2Ph, (S)-CH2Ph Figure 1. 2 = (S)-Me Synthetic methodology allowed for the preparation of structurally related compounds in which planar and central chirality are independently varied. Thus accessible families of closely related ligands enabled us to evaluate the influence of individual molecular parts on the course of asymmetric allylic alkylation of racemic (E)-1,3-diphenylprop-2-en-1-yl acetate with malonate esters. 4 eferences 1. (a) T. Hayashi: Asymmetric Catalysis with Chiral rrocenylphosphine Ligands in rrocenes; A. Togni, T. Hayashi, Eds.; VCH: Weinheim, Germany, 1995; pp (b) Part 1 rrocene Ligands in rrocenes: Ligands, Materials and Biomolecules; P. Štěpnička, Ed.; Wiley: Chichester, UK, 2008; pp M. Lamač, I. Císařová, P. Štěpnička, Eur. J. Inorg. Chem. 2007, M. Lamač, J. Tauchman, I. Císařová, P. Štěpnička, rganometallics 2007, 26, (a) B. M. Trost, D. L. Van Vranken, Chem. ev. 1996, 96, (b) B. M. Trost, M. L. Crawley, Chem. ev. 2003, 103,

23 Transition Metal Pincer Complexes based on Aminophosphines Synthesis and Applications Karl Kirchner* and David Benito-Garagorri Institute of Applied Synthetic Chemistry and Institute of Chemical Technologies and Analytics, Vienna University of Technology, Getreidemarkt 9, A-1060 Wien. ne of the ways of modifying and controlling the properties of transition metal complexes is the use of so-called pincer ligands. This class of tridentate ligands has found numerous applications in various areas of chemistry, including catalysis, due to their combination of stability, activity and variability. Focusing on pincer ligands featuring phosphines as donor groups, the lack of a general method for the preparation of both neutral (PP) and anionic (PCP) pincer ligands using similar precursor compounds as well as the difficulty of introducing chirality into the structure of pincer ligands prompted us to investigate the use of amines as spacers between the aromatic ring and the phosphines. By introducing aminophosphine and phosphoramidite moieties into their structure, the synthesis of both PP and PCP ligands can be achieved via simple condensation reactions. This has resulted in the preparation of a range of new pincer complexes, including various iron complexes which exhibit unusual properties both in the solid state and in solution. The use of some of these complexes as catalysts in different C-C coupling reactions has also been investigated. This lecture presents an overview of ongoing research in the field of aminophosphine-based pincer complexes with emphasis on iron chemistry. eferences 1. Benito-Garagorri, D.; Kirchner, K. Acc. Chem. es. 2008, 41, Benito-Garagorri, D., Puchberger, M.; Mereiter, K.; Kirchner, K. Angew. Chem., Int. Ed., 2008, 47,

24 Mo-Catalyzed Cross-Metathesis eaction of Propynylferrocene T. Bobula, a J. Hudlický, a P. ovák, a. Gyepes, b P. Štěpnička,* b and M. Kotora* a,c a Department of rganic and uclear Chemistry, Faculty of Science, Charles University, Hlavova 8, Praha 2, Czech epublic. b Department of Inorganic Chemistry, Faculty of Science, Charles University, Hlavova 8, Praha 2, Czech epublic. c Institute of rganic Chemistry and Biochemistry, Academy of Sciences of the Czech epublic, Flemingovo nám. 2, Praha 6, Czech epublic.. tomasbobula@gmail.com We reported that catalysts formed in situ from [Mo(C)6] and halophenols in dichloromethane efficiently promote homo-metathesis reactions of (prop-1-yn-1-yl)ferrocene 1 to bis(ferrocenyl)ethyne. 1 The same catalytic system was found to be also active in crossmetathesis reactions of (prop-1-yn-1-yl)ferrocene 1 with various functionalized alkynes 2. 2 The corresponding alkynylferrocenes were obtained with good selectivity and yields. ptimization of the reaction conditions by changing the phenol component has been carried out, revealing a critical influence of the phenol structure on the reaction yield. 1 Me + Me 2x [Mo(C) 6] (20 mol%) halophenol (1 equiv.) toluene, 120 C 3x x = a, = 4-MeC 6 H 4 - b, = 4-MeC 6 H 4 - c, = C 6 H 5 - d, = 4-PhC 6 H 4 - e, = 4-MeCC 6 H 4 - f, = 4-CF 3 C 6 H 4 - g, = 4-CC 6 H 4 - h, = n-c 6 H 13 - i, = AcCH 2 CH 2 - Figure 1. Cross-metathesis of Propynylferrocene 1 with Alkynes 2. The structures of selected compounds were determined by single-crystal X-ray diffraction, and the results (particularly the crystal packing) were correlated with DFT calculations. In addition, the series of alkynes FcC CC 6 H 4 C-X-4 3 (Fc = ferrocenyl) differing by the substituent X was studied by electrochemical methods, manifesting a good correlation between the redox potential of the ferrocene/ferrocenium couple and the Hammett σ p constants of the remote substituents X. eferences 1. D. ečas, M. Kotora, P. Štěpnička, Collect. Czech. Chem. Commun. 2003, 68, T. Bobula, J. Hudlický, P. ovák,. Gyepes, P. Štěpnička, M. Kotora, Eur. J. Inorg. Chem. 2008,