Organosilanes in Radical Chemistry

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ISBN: 9780471498704 | 047149870X
Cover: Hardcover
Copyright: 2/13/2004

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In recent years silicon-centered radicals have played an important role in organic synthesis, polymer chemistry and material sciences. The aim of this book is to offer for the first time a description of silyl radicals within an interdisciplinary context, connecting structural characteristics and chemical properties to their application in different areas of chemistry. The first time different aspects of silyl radicals have been brought together Excellent reference tool for experienced practitioners of radical and/or silicon chemistry Presents various aspects of these intermediates in an original, comprehensive fashion This book is essential for anyone working in free radical and/or silicon chemistry as well as for those who want to approach these fields for the first time.

Preface	p. x
Acknowledgements	p. xii
Formation and Structures of Silyl Radicals	p. 1
Methods of Generation of Silyl Radicals	p. 1
Structural Properties of Silyl Radicals	p. 4
Chemical Studies	p. 4
Electron Paramagnetic Resonance (EPR) Spectra	p. 6
Crystal Structures	p. 11
UV-Visible Spectra	p. 13
Theoretical Studies	p. 14
References	p. 16
Thermochemistry	p. 19
General Considerations	p. 19
Bond Dissociation Enthalpies	p. 20
Radical Kinetics	p. 20
Photoacoustic Calorimetry	p. 22
Theoretical Data	p. 23
Derived Bond Dissociation Energies	p. 24
Ion Thermochemistry	p. 25
Negative-ion Cycles	p. 25
Hydride-affinity Cycles	p. 27
References	p. 28
Hydrogen Donor Abilities of Silicon Hydrides	p. 31
Carbon-centred Radicals	p. 32
Primary Alkyl Radicals and Free-Radical Clock Methodology	p. 32
Other Types of Carbon-centred Radicals	p. 36
Nitrogen-centred Radicals	p. 38
Oxygen-centred Radicals	p. 39
Alkoxyl Radicals	p. 39
Peroxyl Radicals	p. 41
Aryloxyl and Aroyloxyl Radicals	p. 41
Sulfur-centred Radicals	p. 42
Ketone Triplets	p. 43
Hydrogen Atom: An Example of Gas-phase Kinetics	p. 44
Theoretical Approaches	p. 45
References	p. 46
Reducing Agents	p. 49
General Aspects of Radical Chain Reactions	p. 49
Radical-Radical Reactions	p. 51
Radical Initiators	p. 52
Tris(trimethylsilyl)silane	p. 53
Dehalogenations	p. 55
Reductive Removal of Chalcogen Groups (RS and RSe)	p. 59
Deoxygenation of Alcohols (Barton-McCombie Reaction)	p. 62
Miscellaneous Reactions	p. 66
Appendix	p. 69
Other Silicon Hydrides	p. 70
Trialkylsilanes	p. 70
Phenyl Substituted Silicon Hydrides	p. 73
Silyl Substituted Silicon Hydrides	p. 76
Alkylthio Substituted Silicon Hydrides	p. 78
Silicon Hydride/Thiol Mixture	p. 79
Silanethiols	p. 80
Silylated Cyclohexadienes	p. 80
References	p. 82
Addition to Unsaturated Bonds	p. 87
Carbon-Carbon Double Bonds	p. 88
Formation of Silyl Radical Adducts	p. 88
Hydrosilylation of Alkenes	p. 92
Carbon-Carbon Triple Bonds	p. 97
Formation of Silyl Radical Adducts	p. 97
Hydrosilylation of Alkynes	p. 98
Carbon-Oxygen Double Bonds	p. 100
Formation of Silyl Radical Adducts	p. 100
Hydrosilylation of Carbonyl Groups	p. 102
Radical Brook Rearrangement	p. 106
Other Carbon-Heteroatom Multiple Bonds	p. 108
Cumulenes and Hetero-Cumulenes	p. 110
Heteroatom-Heteroatom Multiple Bonds	p. 111
References	p. 115
Unimolecular Reactions	p. 119
Cyclization Reactions of Silyl Radicals	p. 119
Five-membered Ring Expansion	p. 126
Aryl Migration	p. 129
Acyloxy Migration	p. 131
Intramolecular Homolytic Substitution at Silicon	p. 133
Homolytic Organosilicon Group Transfer	p. 137
References	p. 140
Consecutive Radical Reactions	p. 143
Basic Concepts of Carbon-Carbon Bond Formation	p. 143
Intermolecular Formation of Carbon-Carbon Bonds	p. 144
Intramolecular Formation of Carbon-Carbon Bonds (Cyclizations)	p. 149
Construction of Carbocycles	p. 150
Construction of Cyclic Ethers and Lactones	p. 154
Construction of Cyclic Amines and Lactames	p. 161
Formation of Carbon-Heteroatom Bonds	p. 168
Other Useful Radical Rearrangements	p. 170
Allylations	p. 172
Application to Tandem and Cascade Radical Reactions	p. 174
References	p. 181
Silyl Radicals in Polymers and Materials	p. 185
Polysilanes	p. 185
Poly(hydrosilane)s and Related Silyl Radicals	p. 186
Oxidation Studies on Silyl-substituted Silicon Hydrides	p. 189
Poly(hydrosilane)s	p. 189
(Me[subscript 3]Si)[subscript 3]SiH and (Me[subscript 3]Si)[subscript 2]Si(H)Me as Model Compounds	p. 190
Functionalization of Poly(hydrosilane)s	p. 194
Halogenation	p. 194
Addition of Unsaturated Compounds	p. 195
Other Useful Radical Reactions	p. 198
Silylated Fullerenes	p. 198
Radical Chemistry on Silicon Surfaces	p. 202
Oxidation of Hydrogen-terminated Silicon Surfaces	p. 205
Halogenation of H--Si(111)	p. 208
Addition of Unsaturated Compounds on H--Si(111)	p. 208
Addition of Alkenes on Si(100) Surfaces	p. 213
Some Examples of Tailored Experiments on Monolayers	p. 215
References	p. 215
List of Abbreviations	p. 219
Subject Index	p. 221
Table of Contents provided by Rittenhouse. All Rights Reserved.

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Organosilanes in Radical Chemistry

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