Hypercarbon Chemistry, Second Edition

465 Pages·2011·11.16 MB·English

by  George A. Olah

HYPERCARBON
CHEMISTRY
HYPERCARBON
CHEMISTRY
Second Edition
GEORGE A. OLAH
G. K. SURYA PRAKASH
KENNETH WADE
ÁRPÁD MOLNÁR
ROBERT E. WILLIAMS
A JOHN WILEY & SONS, INC., PUBLICATION
Copyright © 2011 by John Wiley & Sons, Inc. All rights reserved
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Library of Congress Cataloging-in-Publication Data:
Hypercarbon chemistry / by George A. Olah . . . [et al.]. – 2nd ed.
p. cm.
Includes index.
ISBN 978-0-470-93568-2 (cloth)
1. Carbonium ions. 2. Organometallic chemistry. I. Olah, George A. (George Andrew), 1927-
QD305.C3H97 2011
547.01–dc22
2010044306
Printed in the United States of America
ePDF ISBN 9781118016442
ePub ISBN 9781118016459
oBook ISBN 9781118016466
10 9 8 7 6 5 4 3 2 1
In Memory of the Late Professor William N. Lipscomb
CONTENTS
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 Defi nitions 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
vii
viii CONTENTS
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’ Stx 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
[CB HX]− 122
11 6 6
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 CB Ring Systems 130
x y
3.10. Supraicosahedral Carborane Systems 133
3.11. Conclusions 137
References 137
4. Mixed Metal–Carbon Clusters and Metal Carbides 149
4.1. Introduction 149
4.2. Complexes of C H Ring Systems with a Metal Atom:
n n
Nido-Shaped MC Clusters 150
n
4.3. Metal Complexes of Acyclic Unsaturated Ligands, C H 157
n n+2
CONTENTS ix
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 13C NMR at 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 (CH+) and Its Analogs 195
5
5.4.1. Alkonium Ions Incorporating Bridging Hydrogens
(Protonated Alkanes, C H +) 195
n 2n+3
5.4.1.1. The Methonium Ion (CH+) 196
5
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 (CH+) and Analogs 208
2 7
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
x CONTENTS
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) +-Type Cations 260
5
5.6.2. (CH) 2+-Type Dications 264
6
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 σ Bonds 340
CONTENTS xi
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-Defi cient Metal, Nitrogen,
and Oxygen Centers 377
6.2.9.1. Isomerization, Rearrangement, and
Redistribution of Alkylmetal Compounds 377
6.2.9.2. Rearrangements to Electron-Defi cient
Nitrogen and Oxygen Centers 381
6.3. Electrophilic Reactions of π-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 S 2 Reaction Transition States and
N
Claimed Intermediates 389
6.4.3. Six-Coordinate Hypervalent Compounds 393
6.5. Conclusions 394
References 394
Conclusions and Outlook 417
Index 419
FOREWORD TO THE FIRST
EDITION
The periodic nature of the properties of atoms and the nature and chemistry
of molecules are based on the wave property of matter and the associated
energetics. Concepts including the electron - pair bond between two atoms and
the associated three- dimensional properties of molecules and reactions have
served the chemist well, and will continue to do so in the future.
The completely delocalized bonds of π - aromatic molecules, introduced by
W. H ü ckel, also provided a basis for a rational description of molecular orbitals
in these systems. An extended H ü ckel theory allowed a study of molecular
orbitals throughout chemistry at a certain level of approximation.
The localized multicenter orbital holds a certain intermediate ground, and
is particularly useful when there are more valence orbitals then electrons in a
molecule or transition state. First widely used in the boron hydrides and car-
boranes, these three - center and multicenter orbitals provide a coherent and
consistent description of much of the structure and chemistry of the upper left
side of the periodic table, and of the interactions of metallic ions with other
atoms or molecules.
Skeletal electron counts (the sum of the s tyx numbers), fi rst proposed by
Wade, Mingos, and Rudolph, have also provided a guide for synthesis, and
have given a basis for fi lled bonding description of polyhedral species and their
fragments. Together with the isolobal concept, diverse areas of chemistry have
thereby been unifi ed.
In this book, one sees the remarkable way in which these ideas bring
together structure and reactivity in a great diversity of novel carbon chemistry
and its relationship with that of boron, lithium, hydrogen, the metals, and
others. The authors are to be congratulated.
xiii