Hypercarbon Chemistry

GEORGE A. OLAH, PhD, is the 1994 Nobel Laureate in Chemistry, Founding Director of the Loker Hydrocarbon Research Institute, and Distinguished Loker Chair Professor at the University of Southern California. A pioneer in the hypercarbon chemistry field, Dr. Olah has published numerous papers, books, and monographs. G. K. SURYA PRAKASH, PhD, is the George A. and Judith A. Olah Nobel Laureate Chair Professor and the Director of the Loker Hydrocarbon Research Institute at the University of Southern California.KENNETH WADE, PhD, DSc, FRS, is an Emeritus Professor at the University of Durham, UK and a Senior Fellow of the Loker Hydrocarbon Research Institute at the University of Southern California.ÁRPÁD MOLNÁR, DSc, is an Emeritus Professor at the University of Szeged, Hungary, and a Senior Fellow of the Loker Hydrocarbon Research Institute at the University of Southern California.ROBERT E. WILLIAMS, PhD, is a Senior Fellow of the Loker Hydrocarbon Research Institute at the University of Southern California.

• Foreword to the First Edition xiii Preface to the Second Edition xvPreface to the First Edition xvii1. Introduction: General Aspects 11.1. Aims and Objectives 11.2. Some Definitions 21.3. Structures of Some Typical Hypercarbon Systems 51.4. The Three-Center Bond Concept: Types of Three-Center Bonds 101.5. The Bonding in More Highly Delocalized Systems 211.6. Reactions Involving Hypercarbon Intermediates 26References 312. Carbon-Bridged (Associated) Metal Alkyls 372.1. Introduction 372.2. Bridged Organoaluminum Compounds 412.3. Beryllium and Magnesium Compounds 502.4. Organolithium Compounds 532.5. Organocopper, Silver, and Gold Compounds 582.6. Scandium, Yttrium, and Lanthanide Compounds 622.7. Titanium, Zirconium, and Hafnium Compounds 642.8. Manganese Compounds 662.9. Other Metal Compounds with Bridging Alkyl Groups 682.10. Agostic Systems Containing Carbon–Hydrogen–Metal 3c–2e Bonds 702.11. Conclusions 76References 773. Carboranes and Metallacarboranes 853.1. Introduction 853.2. Carborane Structures and Skeletal Electron Numbers 873.4. MO Treatments of Closo Boranes and Carboranes 1043.5. The Bonding in Nido and Arachno Carboranes 1073.6. Methods of Synthesis and Interconversion Reactions 1113.7. Some Carbon-Derivatized Carboranes 1143.8. Boron-Derivatized Carboranes: Weakly Basic Anions [CB11H6X6]− 1223.9. Metallacarboranes 1233.10. Supraicosahedral Carborane Systems 1333.11. Conclusions 137References 1374. Mixed Metal–Carbon Clusters and Metal Carbides 1494.1. Introduction 1494.2. Complexes of CnHn Ring Systems with a Metal Atom: Nido-Shaped MCn Clusters 1504.3. Metal Complexes of Acyclic Unsaturated Ligands, CnHn+2 1574.4. Complexes of Unsaturated Organic Ligands with Two or More Metal Atoms: Mixed Metal–Carbon Clusters 1604.5. Metal Clusters Incorporating Core Hypercarbon Atoms 1624.6. Bulk Metal Carbides 1734.7. Metallated Carbocations 1764.8. Conclusions 176References 1775. Hypercoordinate Carbocations and Their Borane Analogs 1855.1. General Concept of Carbocations: Carbenium Versus Carbonium Ions 1855.2. Methods of Generating Hypercoordinate Carbocations 1885.3. Methods Used to Study Hypercoordinate Carbocations 1895.4. Methonium Ion (CH5 +) and Its Analogs 1955.5. Homoaromatic Cations 2475.6. Hypercoordinate (Nonclassical) Pyramidal Carbocations 2605.7. Hypercoordinate Heterocations 2665.8. Carbocation–Borane Analogs 2685.9. Conclusions 276References 2776. Reactions Involving Hypercarbon Intermediates 2956.1. Introduction 2956.2. Reactions of Electrophiles with C–H and C–C Single Bonds 2986.3. Electrophilic Reactions of π-Donor Systems 3836.4. Bridging Hypercoordinate Species with Donor Atom Participation 3886.5. Conclusions 394References 394Conclusions and Outlook 417Index 419

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