Hypercarbon chemistry / George A. Olah ... [and others].

Format:

Book

Contributor:

Olah, George A. (George Andrew), 1927-2017.

Language:

English

Subjects (All):

Carbonium ions.

Organometallic chemistry.

Physical Description:

xix, 454 pages : illustrations ; 25 cm

Edition:

Second edition.

Place of Publication:

Hoboken, N.J. : Wiley, [2011]

Summary:

Olah (chemistry, U. of Southern California) et al. provide an updated edition of their text on the chemistry of hydrocarbons: alkanes, alkenes, alkynes, and aromatics. They survey the major types of compounds that contain hydrocarbon and the relationships that link them, the role played by hypercoordinated carbon intermediates in familiar reactions, the ways that bonding in such systems can be described, and how the study of hydrocarbon compounds reveals the mechanisms of many organic reactions. Chapters discuss specific categories such as organometallics, carboranes, carbocations, or transformations that proceed through transient hypercarbon species, with information on fundamental chemistry, including reactivity, selectivity, stereochemistry, and mechanistic factors. Annotation ©2011 Book News, Inc., Portland, OR (booknews.com)

Contents:

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 Bonds 10

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 Containing Carbon-Hydrogen-Metal 3c-2e Bonds 70

2.11 Conclusions 76

References 77

3 Carboranes and Metallacarboranes 85

3.1 Introduction 85

3.2 Carborane Structures and Skeletal Electron Numbers 87

3.2.1 Closo Carboranes 88

3.2.2 Nido and Arachno Carboranes 89

3.2.3 Carbon Sites in Carboranes; Skeletal Connectivities k 97

3.2.4 Skeletal Bond Orders in Boranes and Carboranes 98

3.3 Localized Bond Schemes for Closo Boranes and Carboranes 98

3.3.1 Lipscomb's Styx Rules and Williams' Six Rules 98

3.3.2 Bond Orders and Skeletal Connectivities 100

3.3.3 Bond Networks and Skeletal Connectivities 101

3.3.4 Calculated Charge Distributions and Edge Bond Orders 102

3.4 MO Treatments of Closo Boranes and Carboranes 104

3.5 The Bonding in Nido and Arachno Carboranes 107

3.5.1 Localized Bond Schemes 107

3.5.2 MO Treatments of Nido and Arachno Boranes and Carboranes 108

3.5.3 Some Boron-Free Nido and Arachno Systems 110

3.6 Methods of Synthesis and Interconversion Reactions 111

3.7 Some Carbon-Derivatized Carboranes 114

3.7.1 Carboranyl C-H X Hydrogen-Bonded Systems 114

3.7.2 Carboranyl-Metal Systems 114

3.7.3 Some Aryl-Carboranes 116

3.8 Boron-Derivatized Carboranes: Weakly Basic Anions [CB11H6X6] 122

3.9 Metallacarboranes 123

3.9.1 Structural Types, Electron Counts, and Isolobal Units 123

3.9.2 Predicting Structures from Formulae 126

3.9.3 Metal Complexes of CxBy Ring Systems 130

3.10 Supraicosahedral Carborane Systems 133

3.l1 Conclusions 137

References 137

4 Mixed Metal-Carbon Clusters and Metal Carbides 149

4.l Introduction 149

4.2 Complexes of CnHn Ring Systems with a Metal Atom: 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 More Metal 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 Analogs 185

5.1 General Concept of Carbocations: Carbenium Versus Carbonium Ions 185

5.1.1 Trivalent-Tricoordinate (Classical) Carbenium Ions 186

5.1.2 Hypercoordinate (Nonclassical) Carbonium Ions 187

5.2 Methods of Generating Hypercoordinate Carbocations 188

5.3 Methods Used to Study Hypercoordinate Carbocations 189

5.3.1 Nmr Spectroscopy in Solution 189

5.3.2 13C NMR Chemical Shift Additivity 192

5.3.3 Isotopic Perturbation Method 192

5.3.4 Solid-State 13CNMRat Extremely Low Temperature 193

5.3.5 X-Ray Diffraction 193

5.3.6 Tool of Increasing Electron Demand 194

5.3.7 Esca 194

5.3.8 Low Temperature Solution Calorimetry 195

5.3.9 Quantum Mechanical Calculations 195

5.4 Methonium Ion (CH5+) and Its Analogs 195

5.4.1 Alkonium Ions Incorporating Bridging Hydrogens (Protonated Alkanes, Cn H2n+3+) 195

5.4.1.1 The Methonium Ion (CH5+) 196

5.4.1.2 Multiply-Protonated Methane Ions and their Analogs 202

5.4.1.3 Varied Methane Cations 205

5.4.1.4 Ethonium Ion (C2H7+) and Analogs 208

5.4.1.5 Proponium Ions and Analogs 210

5.4.1.6 Higher Alkonium Ions 211

5.4.1.7 Adamantonium Ions 217

5.4.1.8 Hydrogen-Bridged Cycloalkonium Ions 217

5.4.1.9 Hydrogen-Bridged Acyclic Ions 221

5.4.1.10 Five-Center, Four-Electron Bonding Structures 223

5.4.2 Hypercoordinate Carbocations Containing 3c-2e C C C Bonds 223

5.4.2.1 Cyclopropylmethyl and Cyclobutyl Cations 223

5.4.2.2 The 2-Norbornyl Cation 229

5.4.2.3 The 7-Norbornyl Cation 243

5.4.2.4 The 2-Bicyclo[2.1.1]hexyl Cation 243

5.4.2.5 The Polymethyl 2-Adamantyl Cations 245

5.5 Homoaromatic Cations 247

5.5.1 Monohomoaromatic Cations 247

5.5.2 Bishomoaromatic Cations 249

5.5.3 Trishomoaromatic Cations 256

5.5.4 Three-Dimensional Homoaromaticity 258

5.5.5 Möbius Homoaromaticity 259

5.6 Hypercoordinate (Nonclassical) Pyramidal Carbocations 260

5.6.1 (CH)5+-Type Cations 260

5.6.2 (CH)62+-Type Dications 264

5.7 Hypercoordinate Heterocations 266

5.7.1 Introduction 266

5.7.2 Hydrogen-Bridged Silyl Cations 266

5.7.3 Homoaromatic Heterocations 267

5.8 Carbocation-Borane Analogs 268

5.8.1 Introduction 268

5.8.2 Hypercoordinate Methonium and Boronium Ions 272

5.8.3 Cage Systems 272

5.8.4 Hypercoordinate Onium-Carbonium Dications and Isoelectronic Onium-Boronium Cations 274

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-C Single Bonds 298

6.2.1 Acid-Catalyzed Reactions and Rearrangements of Alkanes, Cycloalkanes, and Related Compounds 298

6.2.1.1 Carbon-Hydrogen and Carbon-Carbon Bond Protolysis 298

6.2.1.2 Isomerization and Rearrangement 307

6.2.1.3 Alkylation 320

6.2.2 Nitration and Nitrosation 325

6.2.3 Halogenation 328

6.2.4 Carbonylation 331

6.2.5 Oxyfunctionalization 332

6.2.5.1 Oxygenation with Hydrogen Peroxide 332

6.2.5.2 Oxygenation with Ozone 334

6.2.5.3 Oxygenation with Other Reagents 337

6.2.6 Sulfuration 339

6.2.7 Reactions of Coordinatively Unsaturated Metal Compounds and Fragments with C-H and C-C Ã Bonds 340

6.2.7.1 Carbon-Hydrogen Bond Insertion 342

6.2.7.2 Carbon-Carbon Bond Insertion 362

6.2.8 Reactions of Singlet Carbenes, Nitrenes, and Heavy Carbene Analogs with C-H and C-C Bonds 371

6.2.9 Rearrangement to Electron-Deficient Metal, Nitrogen, and Oxygen Centers 377

6.2.9.1 Isomerization, Rearrangement, andRedistribution of Alkylmetal Compounds 377

6.2.9.2 Rearrangements to Electron-Deficient Nitrogen and Oxygen Centers 381

6.3 Electrophilic Reactions of À -Donor Systems 383

6.4 Bridging Hypercoordinate Species with Donor Atom Participation 388

6.4.1 Carbocations with 3c-2e Bond 388

6.4.2 Five-Coordinate SN2 Reaction Transition States and Claimed Intermediates 389

6.4.3 Six-Coordinate Hypervalent Compounds 393

6.5 Conclusions 394

References 394.

Notes:

Includes bibliographical references and index.

ISBN:

9780470935682

0470935685

OCLC:

671491792