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Molecular Clusters of the Main Group Elements Matthias Driess, Heinrich No¨th (Eds.) Molecular Clusters of the Main Group Elements Matthias Driess, Heinrich No¨th (Eds.) Molecular Clusters of the Main Group Elements Further Titles of Interest: G. Schmid (Ed.) Nanoparticles From Theory to Application 2003 ISBN 3-527-30507-6 P. Jutzi, U. Schubert (Eds.) Silicon Chemistry From the Atom to Extended Systems 2003 ISBN 3-527-30647-1 P. Braunstein, L. A. Oro, P. R. Raithby (Eds.) Metal Clusters in Chemistry 1999 ISBN 3-527-29549-6 U. Schubert, N. Husing€ Synthesis of Inorganic Materials 2000 ISBN 3-527-29550-X P. Comba, T. W. Hambley Molecular Modeling of Inorganic Compounds 2001 ISBN 3-527-29915-7 Matthias Driess, Heinrich No¨th (Eds.) Molecular Clusters of the Main Group Elements Prof. Matthias Driess 9 This book was carefully produced. Ruhr-Universita¨t Bochum Nevertheless, authors, editors and publisher Fakulta¨tfu¨r Chemie do not warrant the information contained Lehrstuhl fu¨r Anorganische Chemie I: therein to be free of errors. Readers are Cluster- und Koordinations-Chemie advised to keep in mind that statements, 44780 Bochum data, illustrations, procedural details or Germany other items may inadvertently be inaccurate. Prof. Heinrich No¨th Ludwig-Maximilians-Universita¨tMu¨nchen Library of Congress Card No.: applied for Department Chemie A catalogue record for this book is available Butenandt Str. 5-13 (Haus D) from the British Library. 81377 Munich Bibliographic information published by Die Germany Deutsche Bibliothek Die Deutsche Bibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data is available in the Internet at http:// dnb.ddb.de ( 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim All rights reserved (including those of translation in other languages). No part of this book may be reproduced in any form – by photoprinting, microfilm, or any other means – nor transmitted or translated into machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law. Printed in the Federal Republic of Germany. Printed on acid-free paper. Typesetting Asco Typesetters, Hong Kong Printing Strauss Offsetdruck Gmbh, Morlenbach€ Bookbinding Litges & Dopf Buchbinderei GmbH, Heppenheim ISBN 3-527-30654-4 v Contents Preface xiii List of Contributors xv 1 Theory and Concepts in Main-Group Cluster Chemistry 1 R. Bruce King and Paul v. R. Schleyer 1.1 Introduction 1 1.1.1 Three-center Bonding in Boranes: Lipscomb’s Equations of Balance 4 1.1.2 Polyhedral Skeletal Electron Pair Theory: The Wade-Mingos Rules 6 1.1.3 Aromaticity in Three-dimensional Clusters 8 1.1.3.1 From Polygonal Aromatics to Deltahedral Boranes 8 1.1.3.2 Interstitial Polygonal Aromatic–Deltahedral Borane Relationships 11 1.1.3.3 Aromaticity Evaluations of Three-dimensional Structures: Nucleus- Independent Chemical Shift (NICS) 12 1.1.3.4 Spherical Aromaticity 16 1.1.4 Bare Ionic Post-transition Metal Clusters: The Zintl Phases 17 1.1.5 Clusters of the Heavier Group 13 Metals 21 1.1.5.1 Apparently Hypoelectronic Deltahedra in Bare Clusters of Indium and Thallium: Polyhedra with Flattened Vertices 21 1.1.5.2 Organometallic Deltahedral Clusters of the Heavier Group 13 Metals and More Complicated Structures Derived from Deltahedra 23 1.1.5.3 Giant Aluminum Clusters with Shell Structures Consisting of Nested Polyhedra: Pieces of Icosahedral Quasicrystals 28 1.1.6 Conclusion and Outlook 29 References 30 2.1 Homonuclear Boron Clusters 34 H. No¨th 2.1.1 Introduction 34 2.1.2 General Principles and Systematic Naming 35 2.1.2.1 Structures and Bonding 36 2.1.3 Synthetic Methods 45 2.1.3.1 Diborane Pyrolysis 46 vi Contents 2.1.3.2 The Anionic Route 47 2.1.3.3 Platinum-catalyzed Dehydrocoupling 50 2.1.3.4 Cluster Expansion and Cluster Contraction Reactions 52 2.1.4 Chemistry of Selected Polyboranes 52 2.1.4.1 Chemistry of Triborane B3H7 52 2.1.4.2 Chemistry of Tetraboranes 54 2.1.4.2.1 arachno-Tetraborane(10) 54 2.1.4.2.2 Derivatives of nido-Tetraborane(8), B4H8, and closo-Tetraborane(6), B4H6 57 2.1.4.3 Chemistry of Pentaborane(9) 60 2.1.4.4 Chemistry of Decaborane(14) 63 2.1.5 Chemistry of Selected nido- and closo-Polyborane Anions 67 2À 2.1.5.1 Chemistry of closo-B6H6 68 2.1.5.2 Chemistry of the Nonahydro-closo-nonaborate(2À) 71 2.1.5.3 Reaction of Decahydro-closo-decaborate(2À) 72 À 2.1.5.4 Chemistry of the nido-Decaborate B10H13 73 2À 2.1.5.5 Chemistry of Undecahydro-closo-undecaborate B11H11 73 2.1.5.6 Chemistry of the Dodecahydro-closo-dodecaborate 77 2À 2.1.5.6.1 Protonation and Alkylation of B12H12 77 2.1.5.6.2 Halogeno-, Hydroxo-, Alkoxo- and Amine closo-dodecaborates 77 2À 2.1.5.7 Chemistry of B20H18 Anions 80 2.1.6 Substituted Neutral Polyboranes of Type ByXy 84 2.1.6.1 Overview 84 2.1.6.2 Structures 84 2.1.6.3 Synthesis 85 2.1.6.4 Reactions 89 References 90 2.2 Boron Clusters in Medical Applications 95 Detlef Gabel and Yasuyuki Endo 2.2.1 Introduction 95 2.2.2 Dicarba-closo-dodecaborane, C2B10H12, and Derivatives 99 2.2.2.1 Preparation and Reactions of C2B10 Cage Compounds 99 2.2.2.2 Design and Classification of BNCT Reagents Containing C2B10 Cages 100 2.2.2.3 Amino Acids 100 2.2.2.4 Nucleic Acid Precursors 101 2.2.2.5 DNA Binders 103 2.2.2.6 Porphyrins 104 2.2.2.7 Combination of C2B10 and Gadolinium-containing Species 105 2À 2.2.3 Derivatives of the nido-carborane C2B9H12 106 2.2.4 Application of C2B10 for Drug Design 108 2.2.4.1 Properties of C2B10 for Drug Design 108 2.2.4.2 Nuclear Receptor Ligands Bearing C2B10 Cages 110 2.2.5 closo-Boranes 113 Contents vii 2À 2.2.5.1 B12H12 114 2À 2.2.5.1.1 Introduction of Heteroatoms as Substituents of B12H12 114 2À 2.2.5.1.2 Reactivity of B12H11SH 115 2À 2.2.5.1.3 Reactivity of B12H11OH 116 2À 2.2.5.1.4 Reactivity of B12H11NH2 116 2.2.5.1.5 Analytical and Chromatographic Properties 117 2À 2.2.5.1.6 Compounds for BNCT Derived from the B12H12 Cluster 117 2.2.5.2 Azanonaboranes 118 2.2.6 Testing of Compounds for BNCT 119 References 122 2.3 Clusters of the Heavier Group 13 Elements 126 G. Linti, H. Schno¨ckel, W. Uhl and N. Wiberg 2.3.1 Introduction 126 2.3.2 The Metal–Metal Bond 127 xÀ 2.3.3 Boron Analogous Clusters of the Type [EnRn] (x ¼ 0; 1; 2) 129 2.3.3.1 Tetrahedral Cluster Compounds E4R4 130 2.3.3.1.1 Syntheses 130 2.3.3.1.2 Bonding 134 2.3.3.1.3 Structures 136 2.3.3.1.4 Physical Properties 137 2.3.3.1.5 Reactivity 138 2.3.3.2 Miscellaneous (Neutral and Anionic) Cluster Compounds E6R6,E8R8, E9R9,E12R12 141 2.3.4 Metalloid (Neutral and Anionic) Clusters EnRm<n 144 2.3.4.1 Metalloid Clusters AlnRm<n 145 À À 2.3.4.1.1 Al7 ,Al12 , and In12 Clusters 145 2.3.4.1.2 Al14 Cluster 146 2.3.4.1.3 Al69 and Al77 Clusters 146 2.3.4.1.4 Hypothetical b-Aluminum 148 2.3.4.2 Metalloid Gallium Clusters GanRm<n and Related Indium Clusters 150 2.3.4.2.1 The Modifications of Elemental Ga 150 2.3.4.2.2 Ga6 Cluster 152 2.3.4.2.3 Ga8,Ga9 and Related In Clusters 152 2.3.4.2.4 Ga12 Clusters 154 2.3.4.2.5 Ga10,Ga13, and Ga19 Clusters 155 2.3.4.2.6 Ga18,Ga22, and Ga26 Clusters 158 2.3.4.2.7 The Ga84 Cluster 160 2.3.5 Summary and Outlook 162 References 163 2.4 Discrete and Extended Metal Clusters in Alloys With Mercury and Other Group 12 Elements 169 Hans-Jo¨rg Deiseroth 2.4.1 Introduction 169 viii Contents 2.4.2 Mercuride Clusters in Amalgams – Conflicts With Zintl’s Concept? 170 2.4.2.1 General 170 2.4.2.2 Small Mercuride Clusters 173 2.4.2.3 Single ‘‘Mercuride’’ Ions? 176 2.4.2.4 Extended Anionic Partial Structures of Mercury 178 2.4.2.5 MHgn Clusters With High Coordination Numbers 181 2.4.2.6 NaK29Hg48 A Complex Ternary Amalgam With Mercury Acting as a Pseudo Group 13 Element [9] 183 2.4.2.7 Electric and Magnetic Properties of Amalgams 185 2.4.3 Conclusions 185 Acknowledgements 186 References 186 2.5 Molecular Cages and Clusters of the Heavier Group 14 Elements (E F Si, Ge, Sn or Pb) of Formula EnRm (n K m) 188 Nils Wiberg and Philip P. Power 2.5.1 Introduction 188 2.5.2 Silicon Species of Formula SinRm ðn b mÞ 189 2.5.2.1 Dimers and Trimers 189 2.5.2.2 Tetramers 189 2.5.2.3 Hexamers and Octamers 191 2.5.3 Germanium Cages and Clusters GenRm ðn b mÞ 193 2.5.3.1 Dimers 193 2.5.3.2 Germanium Trimers 194 2.5.3.3 Germanium Tetramers 196 2.5.3.4 Germanium Hexamers, Octamers and Decamers 197 2.5.4 Tin Cages and Clusters and SnnRm ðn b mÞ 199 2.5.4.1 Dimers, Trimers and Tetramers 199 2.5.4.2 Hexamers, Octamers and Decamers 201 2.5.5 Lead Clusters PbnRn 205 2.5.6 Conclusion 206 References 206 2.6 Homoatomic Cages and Clusters of the Heavier Group 15 Elements: Neutral Species and Cations 209 Ingo Krossing 2.6.1 Introduction 209 2.6.2 Neutral Homonuclear Pnicogen Clusters 211 2.6.2.1 Structures of the Tetrahedral E4 Cages 211 2.6.2.2 Bonding in P4 211 2.6.2.3 Larger Pn Cages (n > 4) 214 2.6.3 Cationic Homonuclear Pnicogen Clusters 216 2.6.3.1 Overview 216 2.6.3.2 Reaction Media and Environment for Bi Cluster Syntheses 217 2.6.3.3 Structurally Characterized Bi Cations [42] 217 Contents ix þ þ 2.6.3.4 What About Gaseous Pn and Asn Cations? 221 þ þ 2.6.3.5 The Stability of Hypothetical Pn and Asn Cations in Condensed Phases 223 2.6.4 Outlook 225 Acknowledgement 225 References 226 2.7 Cages and Clusters of the Chalcogens 230 William S.
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