Olah / Prakash / Williams Hypercarbon Chemistry

2. Auflage 2011
ISBN: 978-1-118-01644-2
Verlag: John Wiley & Sons
Format: PDF
Kopierschutz: Adobe DRM (»Systemvoraussetzungen)

E-Book, Englisch, 480 Seiten, E-Book

The essential new edition of the book that put hypercarbonchemistry on the map
A 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. organometallics,carboranes, carbocations) or transformations that proceed throughtransient hypercarbon species, detailing fundamental chemistry,including reactivity, selectivity, stereochemistry, mechanisticfactors and more.

Autoren/Hrsg.

Olah, George A.

Prakash, G. K. Surya

Williams, Robert E.

Wade, Kenneth

Molnár, Árpád

Inhaltsverzeichnis

Foreword to the First Edition xiii
Preface to the Second Edition xv
Preface to the First Edition xvii
1. Introduction: General Aspects 1
1.1. Aims and Objectives 1
1.2. Some Definitions 2
1.3. Structures of Some Typical Hypercarbon Systems 5
1.4. The Three-Center Bond Concept: Types of Three-Center Bonds10
1.5. The Bonding in More Highly Delocalized Systems 21
1.6. Reactions Involving Hypercarbon Intermediates 26
References 31
2. Carbon-Bridged (Associated) Metal Alkyls 37
2.1. Introduction 37
2.2. Bridged Organoaluminum Compounds 41
2.3. Beryllium and Magnesium Compounds 50
2.4. Organolithium Compounds 53
2.5. Organocopper, Silver, and Gold Compounds 58
2.6. Scandium, Yttrium, and Lanthanide Compounds 62
2.7. Titanium, Zirconium, and Hafnium Compounds 64
2.8. Manganese Compounds 66
2.9. Other Metal Compounds with Bridging Alkyl Groups 68
2.10. Agostic Systems ContainingCarbon-Hydrogen-Metal 3c-2e Bonds70
2.11. Conclusions 76
References 77
3. Carboranes and Metallacarboranes 85
3.1. Introduction 85
3.2. Carborane Structures and Skeletal Electron Numbers 87
3.4. MO Treatments of Closo Boranes and Carboranes104
3.5. The Bonding in Nido and Arachno Carboranes107
3.6. Methods of Synthesis and Interconversion Reactions 111
3.7. Some Carbon-Derivatized Carboranes 114
3.8. Boron-Derivatized Carboranes: Weakly Basic Anions[CB11H6X6]- 122
3.9. Metallacarboranes 123
3.10. Supraicosahedral Carborane Systems 133
3.11. Conclusions 137
References 137
4. Mixed Metal-Carbon Clusters and Metal Carbides149
4.1. Introduction 149
4.2. Complexes of CnHn Ring Systems with a MetalAtom: Nido-Shaped MCn Clusters 150
4.3. Metal Complexes of Acyclic Unsaturated Ligands,CnHn+2 157
4.4. Complexes of Unsaturated Organic Ligands with Two or MoreMetal Atoms: Mixed Metal-Carbon Clusters 160
4.5. Metal Clusters Incorporating Core Hypercarbon Atoms 162
4.6. Bulk Metal Carbides 173
4.7. Metallated Carbocations 176
4.8. Conclusions 176
References 177
5. Hypercoordinate Carbocations and Their Borane Analogs185
5.1. General Concept of Carbocations: Carbenium Versus CarboniumIons 185
5.2. Methods of Generating Hypercoordinate Carbocations 188
5.3. Methods Used to Study Hypercoordinate Carbocations 189
5.4. Methonium Ion (CH5 ¯+) and Its Analogs195
5.5. Homoaromatic Cations 247
5.6. Hypercoordinate (Nonclassical) Pyramidal Carbocations260
5.7. Hypercoordinate Heterocations 266
5.8. Carbocation-Borane Analogs 268
5.9. Conclusions 276
References 277
6. Reactions Involving Hypercarbon Intermediates 295
6.1. Introduction 295
6.2. Reactions of Electrophiles with C-H and C-CSingle Bonds 298
6.3. Electrophilic Reactions of pi-Donor Systems 383
6.4. Bridging Hypercoordinate Species with Donor AtomParticipation 388
6.5. Conclusions 394
References 394
Conclusions and Outlook 417
Index 419

Über Autor(innen)

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