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Experimental and Theoretical Study of the Polynuclear Bismuth Compounds – Dimers, Clusters, Molecular Self-Assemblies and Polyhedral Cage Molecules

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Experimental and Theoretical Study of the Polynuclear Bismuth Compounds – Dimers, Clusters, Molecular Self-Assemblies and Polyhedral Cage Molecules INAUGURAL – DISSERTATION zur Erlangung der Doktorwürde der Naturwissenschaftlich-Mathematischen Gesamtfakultät der Ruprecht-Karls-Universität Heidelberg vorgelegt von Kirill Yu. Monakhov (M.Sc.) aus Moskau, Russland Tag der mündlichen Prüfung: 2. Juli 2010 Experimental and Theoretical Study of the Polynuclear Bismuth Compounds – Dimers, Clusters, Molecular Self-Assemblies and Polyhedral Cage Molecules Gutachter: Prof. Dr. Gerald Linti Prof. Dr. Hans-Jörg Himmel Die vorliegende Arbeit wurde in der Zeit von November 2007 bis Mai 2010 am Institut für Anorganische Chemie der Ruprecht-Karls-Universität Heidelberg unter Anleitung von Herrn Prof. Dr. Gerald Linti durchgeführt. Meinen Eltern und Großeltern, meinem Bruder, Mariam und ihrer Mutter Irène gewidmet «Die wahre Wissenschaft und das wahre Studium des Menschen ist der Mensch» Pierre Charron, »Le traité de la sagesse« List of Publications Following topics of this thesis are prepared to be published: 11. Aromaticity of indium and bismuth cluster compounds. G. Linti, K. Yu. Monakhov, M. Bühler, T. Zessin, Graduate College 850 Book 2010, manuscript in preparation. 10. Molecular self-assemblies based on (C5Me5)BiX2 units (X = halogen): synthesis, X-ray crystal structures and quantum chemical study. K. Yu. Monakhov, T. Zessin, G. Linti, manuscript in preparation. 9. Seven-vertex cage cluster Bi4[μ3-Fe(CO)3]3 with π-coordinated aromatic ligands and inverted sandwich behavior in the crystal. K. Yu. Monakhov, T. Zessin, G. Linti, manuscript in preparation. Following topics of this thesis have been published during the doctorate period: 8. Cubane-like bismuth-iron cluster: synthesis, X-ray crystal structure and theoretical 4– characterization of [Bi4Fe8(CO)28] anion. K. Yu. Monakhov, T. Zessin, G. Linti, Eur. J. Inorg. Chem. 2010, in print. 7. Reduction vs. metathesis in the reactions of bismuth tribromide with bulky lithium silanide – an experimental and theoretical study. K. Yu. Monakhov, T. Zessin, G. Linti, Eur. J. Inorg. Chem. 2010, 322–332. 6. Theoretical study of structure, bonding and electronic behavior of low-valent bismuth cyclopentadienyl and pentamethylcyclopentadienyl half-sandwich compounds. K. Yu. Monakhov, G. Linti, Inorg. Chem. 2009, 48, 6986–6996. Following topics based on works in the group 13 metals have been published or submitted: 5. Linked cluster compounds "transition metal - group 13 metals": synthesis, structure characterization and DFT study. E. V. Grachova, G. Linti, K. Yu. Monakhov, T. Zessin, Eur. J. Inorg. Chem. 2010, submitted. 4. Synthesis and structure of Tri- and octaindium compounds. G. Linti, M. Bühler, K. Yu. Monakhov, T. Zessin, Dalton Trans. 2009, 8071–8078. Following topics have been published during the master period: 3. Synthesis and solution behavior of the trinuclear palladium(II) unsaturated carboxylate complexes triangle-Pd3[μ-OCO(R’)C=CHMe]6 (R’ = Me, H), and X-ray structure of palladium(II) tiglate (R’ = Me). T. A. Stromnova, K. Yu. Monakhov, J. Cámpora, P. Palma, E. Carmona, E. Álvarez, Inorg. Chim. Acta 2007, 360, 4111–4116. 2. A quantum-chemical study of donor-acceptor properties of carboxylic acids and their anions, and evaluation of the effect of these properties on geometric and spectroscopic parameters of palladium(II) carboxylates. K. Yu. Monakhov, T. A. Stromnova, Russ. J. Gen. Chem. 2007, 77, 1841–1849; 2008, 77, 1896–1903 (Engl. Transl.). 1. Palladium(I) carbonyl carboxylate clusters cyclo-[Pd2(µ-CO)2(µ-OCOR)2]n (n = 2 or 3): structure and reactivity. T. A. Stromnova, O. N. Shishilov, M. V. Dayneko, K. Yu. Monakhov, A. V. Churakov, L. G. Kuz’mina, J. A. K. Howard, J. Organomet. Chem. 2006, 691, 3730–3736. Talks and Poster Presentations 1. K. Yu. Monakhov, T. Zessin, G. Linti. – "Polyhedral bismuth cages stabilized by organic and inorganic ligands". // Challenges in Inorganic and Materials Chemistry, 20–23 July 2010, Hong Kong, China. 2. K. Yu. Monakhov, G. Linti. – "Theoretical study of structure, bonding and electronic behavior of low-valent bismuth cyclopentadienyl and pentamethylcyclopentadienyl half- sandwich compounds". // Summer School in Computational Chemistry, 22–26 September 2009, Essen, Germany. 3. K. Yu. Monakhov, G. Linti, E. V. Grachova. – "The problem of metal centers interaction in mixed-metal bridging complexes containing transition metal and group 13 metal". // XXIVth International Chugaev Conference on Coordination Chemistry, 15–19 June 2009, St. Petersburg, Russia. Book of Abstracts, p. 414. 4. K. Yu. Monakhov, G. Linti. – "The precursors for the synthesis of indium and bismuth silyl-substituted compounds". // VIth International Congress of Young Chemists, 15–19 October 2008, Cracow, Poland. Book of Abstracts, p. 131. 5. K. Yu. Monakhov, G. Linti. – "Theoretical investigation of Bi∙∙∙C5R5 (R = H, Me) interactions in bismuth (I, III, V) cyclopentadienyl and pentamethylcyclopentadienyl complexes". // 44th Symposium on Theoretical Chemistry, 23–27 September, 2008, Ramsau am Dachstein, Austria. Book of Abstracts, P-15. 6. K. Yu. Monakhov, T. A. Stromnova. – "Prochiral palladium carboxylates: synthesis, structures and properties". // XXIIIth International Chugaev Conference on Coordination Chemistry, 4–7 September 2007, Odessa, Ukraine. Book of Abstracts, pp. 540–541. 7. K. Yu. Monakhov, T. A. Stromnova. – "Unsaturated carboxylic acids as polyfunctional ligands in chemistry of the platinum metals". // The XIVth International Scientific Conference for Undergraduate and Postgraduate Students, and Young Scientists «Lomonosov-2007», 11–14 April 2007, Moscow, Russia. Book of Abstracts, p. 252. Danksagung Zuallererst möchte ich mich ganz herzlich bei meinem Doktorvater Prof. Dr. Gerald Linti für die interessante Themenstellung und die wissenschaftlichen Freiheiten, für das fortwährende Interesse an meiner Arbeit und die wissenschaftliche Förderung bedanken. Auch bedanke ich mich bei meinen Laborkollegen, namentlich Thomas Zessin, Philipp Butzug, Dominik Scheid, Marc Herrmann, Dr. Tobias Adamczyk, Dr. Annekathrin Seifert und Dr. Ovidiu Feier-Iova für ein produktives und angenehmes Arbeiten und für das freundliche Arbeitsklima. Insbesondere möchte ich Thomas und Philipp für ihre Hilfe bei den alltäglichen Problemen im Labor und für das Messen und die Lösung der Röntgenstrukturen „Vielen Dank“ sagen. Frau Dr. Elena Grachova (Department of Chemistry, St. Petersburg State University) und Herrn Dr. Alexander A. Auer (Atomistic Modeling Group, Max Planck Institute for Iron Research in Düsseldorf) danke ich für die hilfsreichen Diskussionen zu meiner Chemie und die wertvollen Ratschläge. Bei Frau Dr. Elena Grachova bedanke ich mich nochmals für eine produktive Zusammenarbeit im Bereich Übergangsmetalle und Hauptgruppenelemente. Herzlichen Dank an Frau Karin Stelzer und Frau Marlies Schönebeck-Schilli für die groβe Hilfe und Unterstützung bei allen Verwaltungsangelegenheiten. Vielen Dank auch allen, die direkt oder indirekt zum Gelingen der Arbeit beigetragen haben: meinem Forschungspraktikanten Johannes Straub; allen Mitarbeitern der chemischen Institute, insbesondere Herrn Dr. Jürgen Gross und seinen Mitarbeitern für die Massenspektrometrie- daten; Frau Beate Termin für das Messen der NMR-Spektren; dem gesamten Arbeitskreis „Comba“ für eine gute Atmosphäre am Institut für Anorganische Chemie und ihre Hilfsbereitschaft; allen Mitgliedern des Graduiertenkollegs 850 für eine schöne gemeinsame Zeit im Studium. Des Weiteren bedanke ich mich bei dem Graduiertenkolleg 850 der Deutschen Forschungsgemeinschaft für das Stipendium. Schließlich gilt mein ganz besonders herzlicher Dank meinen Eltern Natalia und Yuri Monakhov, meinem Bruder Artem, meinen Groβeltern, meiner schönen Freundin Mariam Mainguy und ihrer Mutter Irène Mainguy, die mir durch ihre moralische Unterstützung während meiner wissenschaftlichen Arbeit in Heidelberg geholfen haben. Contents Abbreviations and Symbols 1 Abstract 3 Zusammenfassung 4 Chapter 1. Introduction 6 1.1 The heaviest element (Bi) of the group 15 elements and its chemistry 6 1.2 Nomenclature of bismuth compounds 10 1.3 Element–element relationships 10 1.3.1 What is cluster? 10 1.3.2 What are poly-, homo- and heteronuclear metal compounds? 11 1.3.3 Bonding concept by Lipscomb 11 1.3.4 Topologies of clusters 12 1.3.5 Principle of isolobality 13 1.3.6 Principle of isoelectronicity 13 1.3.7 Theoretical and computational approach 13 1.4 Aim of the thesis 15 1.5 References 16 Chapter 2. Bismuth–Bismuth Bonding 19 2.1 Introduction 19 2.1.1 Dibismuthanes 19 2.1.2 Monovalent organobismuth compounds 21 2.1.3 References 27 2.2 Silyl-substituted bismuth compounds 28 2.2.1 Introduction 28 2.2.2 Reduction vs. metathesis in the reactions of BiBr3 with Li(thf)3SiPh2tBu 29 2.2.2.1 Syntheses and spectroscopic characterization of (tBuPh2Si)4Bi2 and (tBuPh2Si)2BiBr 29 2.2.2.2 X-ray crystal structure of Li(thf)3SiPh2tBu 30 2.2.2.3 X-ray crystal structure of (tBuPh2Si)4Bi2 31 2.2.2.4 X-ray crystal structure of (tBuPh2Si)2BiBr 34 2.2.3 Quantum chemical study of bismuthanes and dibismuthanes 35 2.2.3.1 Pyramidal (R3Si)3Bi structures 35 I 2.2.3.2 Pnicogen radicals (H3Si)2E· and their dimers 36 2.2.3.3 N-merization of n·(H3A)2Bi· radicals and oligomerization of dimers 39 2.2.3.4 NBO analysis 42 2.2.3.5 Results from molecular orbital theory 43 2.2.3.6 TD-DFT computations 45 2.2.4 Conclusions 46 2.2.5 References 48 2.3 Appendix to chapter 2.2 50 2.3.1 Evaluation of the effects of an solvent complexation on the geometric, bonding, electronic and energetic characteristics of lithium tert- butyldiphenylsilanides 50 2.3.2
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