Hypercarbon Chemistry
, by Olah, George A.; Prakash, G. K. Surya; Williams, Robert E.; Wade, Kenneth; Molná r, Á rpá dNote: Supplemental materials are not guaranteed with Rental or Used book purchases.
- ISBN: 9780470935682 | 0470935685
- Cover: Hardcover
- Copyright: 8/9/2011
This book is a comprehensive and contemporary treatment of the chemistry of alkanes, alkenes, dienes, acetylenes and aromatics. It covers all major aspects of the chemistry involved in hydrocarbon transformations. Each chapter deals with a specific type of transformation and details all related fundamental chemistry, including reactivity, selectivity, stereochemical considerations, mechanistic factors and practical applications. Chemical formulas and flow sheets assist readers in understanding discussions.
Geoge 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. rpd Molnr, DSc, is an Emeritus Professor at the University of Szissed Hungary and a Senior Fellow of the Loker Hydrocarbon Research Institute at the University of Southern California. Robert E. Williams, Ph.d, is a Senior Fellow of the Loker Hydrocarbon Research Institute at the University of Southern California.
Foreword to the First Edition | p. xiii |
Preface to the Second Edition | p. xv |
Preface to the First Edition | p. xvii |
Introduction: General Aspects | p. 1 |
Aims and Objectives | p. 1 |
Some Definitions | p. 2 |
Structures of Some Typical Hypercarbon Systems | p. 5 |
The Three-Center Bond Concept: Types of Three-Center Bonds | p. 10 |
The Bonding in More Highly Delocalized Systems | p. 21 |
Reactions Involving Hypercarbon Intermediates | p. 26 |
References | p. 31 |
Carbon-Bridged (Associated) Metal Alkyls | p. 37 |
Introduction | p. 37 |
Bridged Organoaluminum Compounds | p. 41 |
Beryllium and Magnesium Compounds | p. 50 |
Organolithium Compounds | p. 53 |
Organocopper, Silver, and Gold Compounds | p. 58 |
Scandium, Yttrium, and Lanthanide Compounds | p. 62 |
Titanium, Zirconium, and Hafnium Compounds | p. 64 |
Manganese Compounds | p. 66 |
Other Metal Compounds with Bridging Alkyl Groups | p. 68 |
Agostic Systems Containing Carbon-Hydrogen-Metal 3c-2e Bonds | p. 70 |
Conclusions | p. 76 |
References | p. 77 |
Carboranes and Metallacarboranes | p. 85 |
Introduction | p. 85 |
Carborane Structures and Skeletal Electron Numbers | p. 87 |
Closo Carboranes | p. 88 |
Nido and Arachno Carboranes | p. 89 |
Carbon Sites in Carboranes; Skeletal Connectivities k | p. 97 |
Skeletal Bond Orders in Boranes and Carboranes | p. 98 |
Localized Bond Schemes for Closo Boranes and Carboranes | p. 98 |
Lipscomb's Styx Rules and Williams' Six Rules | p. 98 |
Bond Orders and Skeletal Connectivities | p. 100 |
Bond Networks and Skeletal Connectivities | p. 101 |
Calculated Charge Distributions and Edge Bond Orders | p. 102 |
MO Treatments of Closo Boranes and Carboranes | p. 104 |
The Bonding in Nido and Arachno Carboranes | p. 107 |
Localized Bond Schemes | p. 107 |
MO Treatments of Nido and Arachno Boranes and Carboranes | p. 108 |
Some Boron-Free Nido and Arachno Systems | p. 110 |
Methods of Synthesis and Interconversion Reactions | p. 111 |
Some Carbon-Derivatized Carboranes | p. 114 |
Carboranyl C-H X Hydrogen-Bonded Systems | p. 114 |
Carboranyl-Metal Systems | p. 114 |
Some Aryl-Carboranes | p. 116 |
Boron-Derivatized Carboranes: Weakly Basic Anions [CB11H6X6] | p. 122 |
Metallacarboranes | p. 123 |
Structural Types, Electron Counts, and Isolobal Units | p. 123 |
Predicting Structures from Formulae | p. 126 |
Metal Complexes of CxBy Ring Systems | p. 130 |
Supraicosahedral Carborane Systems | p. 133 |
Conclusions | p. 137 |
References | p. 137 |
Mixed Metal-Carbon Clusters and Metal Carbides | p. 149 |
Introduction | p. 149 |
Complexes of CnHn Ring Systems with a Metal Atom: Nido-Shaped MCn Clusters | p. 150 |
Metal Complexes of Acyclic Unsaturated Ligands, CnHn+2 | p. 157 |
Complexes of Unsaturated Organic Ligands with Two or More Metal Atoms: Mixed Metal-Carbon Clusters | p. 160 |
Metal Clusters Incorporating Core Hypercarbon Atoms | p. 162 |
Bulk Metal Carbides | p. 173 |
Metallated Carbocations | p. 176 |
Conclusions | p. 176 |
References | p. 177 |
Hypercoordinate Carbocations and Their Borane Analogs | p. 185 |
General Concept of Carbocations: Carbenium Versus Carbonium Ions | p. 185 |
Trivalent-Tricoordinate (Classical) Carbenium Ions | p. 186 |
Hypercoordinate (Nonclassical) Carbonium Ions | p. 187 |
Methods of Generating Hypercoordinate Carbocations | p. 188 |
Methods Used to Study Hypercoordinate Carbocations | p. 189 |
Nmr Spectroscopy in Solution | p. 189 |
13C NMR Chemical Shift Additivity | p. 192 |
Isotopic Perturbation Method | p. 192 |
Solid-State 13CNMRat Extremely Low Temperature | p. 193 |
X-Ray Diffraction | p. 193 |
Tool of Increasing Electron Demand | p. 194 |
Esca | p. 194 |
Low Temperature Solution Calorimetry | p. 195 |
Quantum Mechanical Calculations | p. 195 |
Methonium Ion (CH5+) and Its Analogs | p. 195 |
Alkonium Ions Incorporating Bridging Hydrogens (Protonated Alkanes, Cn H2n+3+) | p. 195 |
The Methonium Ion (CH5+) | p. 196 |
Multiply-Protonated Methane Ions and their Analogs | p. 202 |
Varied Methane Cations | p. 205 |
Ethonium Ion (C2H7+) and Analogs | p. 208 |
Proponium Ions and Analogs | p. 210 |
Higher Alkonium Ions | p. 211 |
Adamantonium Ions | p. 217 |
Hydrogen-Bridged Cycloalkonium Ions | p. 217 |
Hydrogen-Bridged Acyclic Ions | p. 221 |
Five-Center, Four-Electron Bonding Structures | p. 223 |
Hypercoordinate Carbocations Containing 3c-2e C C C Bonds | p. 223 |
Cyclopropylmethyl and Cyclobutyl Cations | p. 223 |
The 2-Norbornyl Cation | p. 229 |
The 7-Norbornyl Cation | p. 243 |
The 2-Bicyclo[2.1.1]hexyl Cation | p. 243 |
The Polymethyl 2-Adamantyl Cations | p. 245 |
Homoaromatic Cations | p. 247 |
Monohomoaromatic Cations | p. 247 |
Bishomoaromatic Cations | p. 249 |
Trishomoaromatic Cations | p. 256 |
Three-Dimensional Homoaromaticity | p. 258 |
Möbius Homoaromaticity | p. 259 |
Hypercoordinate (Nonclassical) Pyramidal Carbocations | p. 260 |
(CH)5+-Type Cations | p. 260 |
(CH)62+-Type Dications | p. 264 |
Hypercoordinate Heterocations | p. 266 |
Introduction | p. 266 |
Hydrogen-Bridged Silyl Cations | p. 266 |
Homoaromatic Heterocations | p. 267 |
Carbocation-Borane Analogs | p. 268 |
Introduction | p. 268 |
Hypercoordinate Methonium and Boronium Ions | p. 272 |
Cage Systems | p. 272 |
Hypercoordinate Onium-Carbonium Dications and Isoelectronic Onium-Boronium Cations | p. 274 |
Conclusions | p. 276 |
References | p. 277 |
Reactions Involving Hypercarbon Intermediates | p. 295 |
Introduction | p. 295 |
Reactions of Electrophiles with C-H and C-C Single Bonds | p. 298 |
Acid-Catalyzed Reactions and Rearrangements of Alkanes, Cycloalkanes, and Related Compounds | p. 298 |
Carbon-Hydrogen and Carbon-Carbon Bond Protolysis | p. 298 |
Isomerization and Rearrangement | p. 307 |
Alkylation | p. 320 |
Nitration and Nitrosation | p. 325 |
Halogenation | p. 328 |
Carbonylation | p. 331 |
Oxyfunctionalization | p. 332 |
Oxygenation with Hydrogen Peroxide | p. 332 |
Oxygenation with Ozone | p. 334 |
Oxygenation with Other Reagents | p. 337 |
Sulfuration | p. 339 |
Reactions of Coordinatively Unsaturated Metal Compounds and Fragments with C-H and C-C Ã Bonds | p. 340 |
Carbon-Hydrogen Bond Insertion | p. 342 |
Carbon-Carbon Bond Insertion | p. 362 |
Reactions of Singlet Carbenes, Nitrenes, and Heavy Carbene Analogs with C-H and C-C Bonds | p. 371 |
Rearrangement to Electron-Deficient Metal, Nitrogen, and Oxygen Centers | p. 377 |
Isomerization, Rearrangement, andRedistribution of Alkylmetal Compounds | p. 377 |
Rearrangements to Electron-Deficient Nitrogen and Oxygen Centers | p. 381 |
Electrophilic Reactions of À -Donor Systems | p. 383 |
Bridging Hypercoordinate Species with Donor Atom Participation | p. 388 |
Carbocations with 3c-2e Bond | p. 388 |
Five-Coordinate SN2 Reaction Transition States and Claimed Intermediates | p. 389 |
Six-Coordinate Hypervalent Compounds | p. 393 |
Conclusions | p. 394 |
References | p. 394 |
Conclusions and Outlook | p. 417 |
Index | p. 419 |
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