The essential new edition of the book that put hypercarbon chemistry on the map A comprehensive and contemporary treatment of the chemistry of hydrocarbons (alkanes, alkenes, alkynes, and aromatics) towards electrophiles, Hypercarbon Chemistry, Second Edition deals with all major aspects of such chemistry involved in hydrocarbon transformations, and of the structural and reaction chemistry of carboranes, mixed hydrides in which both carbon and boron atoms participate in the polyhedral molecular frameworks. Despite the firmly established tetravalency, carbon can bond simultaneously to five or more other atoms. "e;Hypercarbon"e; bonding permeates much organic, inorganic and organometallic chemistry, and the book serves as the compendium for this phenomenon. Copious diagrams illustrate the rich variety of hypercarbon structures now known, and patterns therein. Individual chapters deal with specific categories of compound (e.g. organometallics, carboranes, carbocations) or transformations that proceed through transient hypercarbon species, detailing fundamental chemistry, including reactivity, selectivity, stereochemistry, mechanistic factors and more.

The essential new edition of the book that put hypercarbonchemistry on the mapA comprehensive and contemporary treatment of the chemistry ofhydrocarbons (alkanes, alkenes, alkynes, and aromatics) towardselectrophiles, Hypercarbon Chemistry, Second Edition dealswith all major aspects of such chemistry involved in hydrocarbontransformations, and of the structural and reaction chemistry ofcarboranes, mixed hydrides in which both carbon and boron atomsparticipate in the polyhedral molecular frameworks.Despite the firmly established tetravalency, carbon can bondsimultaneously to five or more other atoms. "Hypercarbon" bondingpermeates much organic, inorganic and organometallic chemistry, andthe book serves as the compendium for this phenomenon.Copious diagrams illustrate the rich variety of hypercarbonstructures now known, and patterns therein. Individual chaptersdeal with specific categories of compound (e.g. organometallicscarboranes, carbocations) or transformations that proceed throughtransient hypercarbon species, detailing fundamental chemistryincluding reactivity, selectivity, stereochemistry, mechanisticfactors and more.

Foreword to the First Edition xiiiPreface 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 Bonds101.5. 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 ContainingCarbon-Hydrogen-Metal 3c-2e Bonds702.11. 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 Carboranes1043.5. The Bonding in Nido and Arachno Carboranes1073.6. 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 Carbides1494.1. Introduction 1494.2. Complexes of CnHn Ring Systems with a MetalAtom: Nido-Shaped MCn Clusters 1504.3. Metal Complexes of Acyclic Unsaturated LigandsCnHn+2 1574.4. Complexes of Unsaturated Organic Ligands with Two or MoreMetal 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 Analogs1855.1. General Concept of Carbocations: Carbenium Versus CarboniumIons 1855.2. Methods of Generating Hypercoordinate Carbocations 1885.3. Methods Used to Study Hypercoordinate Carbocations 1895.4. Methonium Ion (CH5 ¯+) and Its Analogs1955.5. Homoaromatic Cations 2475.6. Hypercoordinate (Nonclassical) Pyramidal Carbocations2605.7. 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-CSingle Bonds 2986.3. Electrophilic Reactions of pi-Donor Systems 3836.4. Bridging Hypercoordinate Species with Donor AtomParticipation 3886.5. Conclusions 394References 394Conclusions and Outlook 417Index 419