HYPERCARBON CHEMISTRY, Second Edition -- CONTENTS -- FOREWORD TO THE FIRST EDITION -- PREFACE TO THE SECOND EDITION -- PREFACE TO THE FIRST EDITION -- 1: INTRODUCTION: GENERAL ASPECTS -- 1.1. AIMS AND OBJECTIVES -- 1.2. SOME DEFINITIONS -- 1.3. STRUCTURES OF SOME TYPICAL HYPERCARBON SYSTEMS -- 1.4. THE THREE-CENTER BOND CONCEPT: TYPES OF THREE-CENTER BONDS -- 1.5. THE BONDING IN MORE HIGHLY DELOCALIZED SYSTEMS -- 1.6. REACTIONS INVOLVING HYPERCARBON INTERMEDIATES -- REFERENCES -- 2: CARBON-BRIDGED (ASSOCIATED) METAL ALKYLS -- 2.1. INTRODUCTION -- 2.2. BRIDGED ORGANOALUMINUM COMPOUNDS -- 2.3. BERYLLIUM AND MAGNESIUM COMPOUNDS -- 2.4. ORGANOLITHIUM COMPOUNDS -- 2.5. ORGANOCOPPER, SILVER, AND GOLD COMPOUNDS -- 2.6. SCANDIUM, YTTRIUM, AND LANTHANIDE COMPOUNDS -- 2.7. TITANIUM, ZIRCONIUM, AND HAFNIUM COMPOUNDS -- 2.8. MANGANESE COMPOUNDS -- 2.9. OTHER METAL COMPOUNDS WITH BRIDGING ALKYL GROUPS -- 2.10. AGOSTIC SYSTEMS CONTAINING CARBON-HYDROGEN-METAL 3c-2e BONDS -- 2.11. CONCLUSIONS -- REFERENCES -- 3: CARBORANES AND METALLACARBORANES -- 3.1. INTRODUCTION -- 3.2. CARBORANE STRUCTURES AND SKELETAL ELECTRON NUMBERS -- 3.2.1. Closo Carboranes -- 3.2.2. Nido and Arachno Carboranes -- 3.2.3. Carbon Sites in Carboranes -- Skeletal Connectivities k -- 3.2.4. Skeletal Bond Orders in Boranes and Carboranes -- 3.3. LOCALIZED BOND SCHEMES FOR CLOSO BORANES AND CARBORANES -- 3.3.1. Lipscomb's Styx Rules and Williams' Stx Rules -- 3.3.2. Bond Orders and Skeletal Connectivities -- 3.3.3. Bond Networks and Skeletal Connectivities -- 3.3.4. Calculated Charge Distributions and Edge Bond Orders -- 3.4. MO TREATMENTS OF CLOSO BORANES AND CARBORANES -- 3.5. THE BONDING IN NIDO AND ARACHNO CARBORANES -- 3.5.1. Localized Bond Schemes -- 3.5.2. MO Treatments of Nido and Arachno Boranes and Carboranes -- 3.5.3. Some Boron-Free Nido and Arachno Systems.

3.6. METHODS OF SYNTHESIS AND INTERCON VERSIONREACTIONS -- 3.7. SOME CARBON-DERIVATIZED CARBORANES -- 3.7.1. Carboranyl C-H- - -X Hydrogen-Bonded Systems -- 3.7.2. Carboranyl-Metal Systems -- 3.7.3. Some Aryl-Carboranes -- 3.8. BORON-DERIVATIZED CARBORANES: WEAKLY BASIC ANIONS [CB11H6X6]− -- 3.9. METALLACARBORANES -- 3.9.1. Structural Types, Electron Counts, and Isolobal Units -- 3.9.2. Predicting Structures from Formulae -- 3.9.3. Metal Complexes of CxBy Ring Systems -- 3.10. SUPRAICOSAHEDRAL CARBORANE SYSTEMS -- 3.11. CONCLUSIONS -- REFERENCES -- 4: MIXED METAL-CARBON CLUSTERS AND METAL CARBIDES -- 4.1. INTRODUCTION -- 4.2. COMPLEXES OF CnHn RING SYSTEMS WITH A METAL ATOM: NIDO-SHAPED MCn CLUSTERS -- 4.3. METAL COMPLEXES OF ACYCLIC UNSATURATED LIGANDS, CnHn+2 -- 4.4. COMPLEXES OF UNSATURATED ORGANIC LIGANDS WITH TWO OR MORE METAL ATOMS: MIXED METAL-CARBON CLUSTERS -- 4.5. METAL CLUSTERS INCORPORATING CORE HYPERCARBON ATOMS -- 4.6. BULK METAL CARBIDES -- 4.7. METALLATED CARBOCATIONS -- 4.8. CONCLUSIONS -- REFERENCES -- 5: HYPERCOORDINATE CARBOCATIONS AND THEIR BORANE ANALOGS -- 5.1. GENERAL CONCEPT OF CARBOCATIONS: CARBENIUM VERSUS CARBONIUM IONS -- 5.1.1. Trivalent-Tricoordinate (Classical) Carbenium Ions -- 5.1.2. Hypercoordinate (Nonclassical) Carbonium Ions -- 5.2. METHODS OF GENERATING HYPERCOORDINATE CARBOCATIONS -- 5.3. METHODS USED TO STUDY HYPERCOORDINATE CARBOCATIONS -- 5.3.1. NMR Spectroscopy in Solution -- 5.3.2. 13C NMR Chemical Shift Additivity -- 5.3.3. Isotopic Perturbation Method -- 5.3.4. Solid-State 13C NMR at Extremely Low Temperature -- 5.3.5. X-Ray Diffraction -- 5.3.6. Tool of Increasing Electron Demand -- 5.3.7. ESCA -- 5.3.8. Low Temperature Solution Calorimetry -- 5.3.9. Quantum Mechanical Calculations -- 5.4. METHONIUM ION (CH5+) AND ITS ANALOGS.

5.4.1. Alkonium Ions Incorporating Bridging Hydrogens (Protonated Alkanes, CnH2n+3+) -- 5.4.1.1. The Methonium Ion (CH5+) -- 5.4.1.2. Multiply-Protonated Methane Ions and their Analogs -- 5.4.1.3. Varied Methane Cations -- 5.4.1.4. Ethonium Ion (C2H7+) and Analogs -- 5.4.1.5. Proponium Ions and Analogs -- 5.4.1.6. Higher Alkonium Ions -- 5.4.1.7. Adamantonium Ions -- 5.4.1.8. Hydrogen-Bridged Cycloalkonium Ions -- 5.4.1.9. Hydrogen-Bridged Acyclic Ions -- 5.4.1.10. Five-Center, Four-Electron Bonding Structures -- 5.4.2. Hypercoordinate Carbocations Containing 3c-2e C- - -C- - -C Bonds -- 5.4.2.1. Cyclopropylmethyl and Cyclobutyl Cations -- 5.4.2.2. The 2-Norbornyl Cation -- 5.4.2.3. The 7-Norbornyl Cation -- 5.4.2.4. The 2-Bicyclo[2.1.1]hexyl Cation -- 5.4.2.5. The Polymethyl 2-Adamantyl Cations -- 5.5. HOMOAROMATIC CATIONS -- 5.5.1. Monohomoaromatic Cations -- 5.5.2. Bishomoaromatic Cations -- 5.5.3. Trishomoaromatic Cations -- 5.5.4. Three-Dimensional Homoaromaticity -- 5.5.5. Möbius Homoaromaticity -- 5.6. HYPERCOORDINATE (NONCLASSICAL) PYRAMIDAL CARBOCATIONS -- 5.6.1. (CH)5+-Type Cations -- 5.6.2. (CH)62+-Type Dications -- 5.7. HYPERCOORDINATE HETEROCATIONS -- 5.7.1. Introduction -- 5.7.2. Hydrogen-Bridged Silyl Cations -- 5.7.3. Homoaromatic Heterocations -- 5.8. CARBOCATION-BORANE ANALOGS -- 5.8.1. Introduction -- 5.8.2. Hypercoordinate Methonium and Boronium Ions -- 5.8.3. Cage Systems -- 5.8.4. Hypercoordinate Onium-Carbonium Dications and Isoelectronic Onium-Boronium Cations -- 5.9. CONCLUSIONS -- REFERENCES -- 6: REACTIONS INVOLVING HYPERCARBON INTERMEDIATES -- 6.1. INTRODUCTION -- 6.2. REACTIONS OF ELECTROPHILES WITH C-H AND C-C SINGLE BONDS -- 6.2.1. Acid-Catalyzed Reactions and Rearrangements of Alkanes, Cycloalkanes, and Related Compounds -- 6.2.1.1. Carbon-Hydrogen and Carbon-Carbon Bond Protolysis.

6.2.1.2. Isomerization and Rearrangement -- 6.2.1.3. Alkylation -- 6.2.2. Nitration and Nitrosation -- 6.2.3. Halogenation -- 6.2.4. Carbonylation -- 6.2.5. Oxyfunctionalization -- 6.2.5.1. Oxygenation with Hydrogen Peroxide -- 6.2.5.2. Oxygenation with Ozone -- 6.2.5.3. Oxygenation with Other Reagents -- 6.2.6. Sulfuration -- 6.2.7. Reactions of Coordinatively Unsaturated Metal Compounds and Fragments with C-H and C-C σ Bonds -- 6.2.7.1. Carbon-Hydrogen Bond Insertion -- 6.2.7.2. Carbon-Carbon Bond Insertion -- 6.2.8. Reactions of Singlet Carbenes, Nitrenes, and Heavy Carbene Analogs with C-H and C-C Bonds -- 6.2.9. Rearrangement to Electron-Deficient Metal, Nitrogen, and Oxygen Centers -- 6.2.9.1. Isomerization, Rearrangement, and Redistribution of Alkylmetal Compounds -- 6.2.9.2. Rearrangements to Electron-Deficient Nitrogen and Oxygen Centers -- 6.3. ELECTROPHILIC REACTIONS OF π-DONOR SYSTEMS -- 6.4. BRIDGING HYPERCOORDINATE SPECIES WITH DONOR ATOM PARTICIPATION -- 6.4.1. Carbocations with 3c-2e Bond -- 6.4.2. Five-Coordinate SN2 Reaction Transition States and Claimed Intermediates -- 6.4.3. Six-Coordinate Hypervalent Compounds -- 6.5. CONCLUSIONS -- REFERENCES -- CONCLUSIONS AND OUTLOOK -- INDEX.