"Front Matter". In: Organosilanes in Radical Chemistry - Index of

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Preface xi but I have not entered into the field of silicon-containing ceramics obtained by chemical vapour deposition techniques, although gaseous silyl radicals are thought to be essential. Since this book mainly deals with the literature on silyl radicals after the 1980s, the references quoted for the early work are not always the seminal ones but the available reviews. I hope that early experts in the field will forgive me if they find their pet paper uncited. I have tried to maintain an essential simplicity and readability of the text, and hope that I have succeeded so that the book is easily consulted also by nonexperts. I also hope that this book serves as an important link between the various areas of chemistry. Chryssostomos Chatgilialoglu Bologna, July 2003
ACKNOWLEDGEMENTS I thank Keith U. Ingold for having introduced me to this subject. When I arrived in Ottawa at the National Research Council of Canada in 1979 for three years’ postdoctoral work with him, very little was known on the reactivity of silyl radicals. At that time, several papers dealing with kinetics of silyl radicals were published, which allowed the reactivity of silyl radical to be translated into a quantitative base. Special thanks go to David Griller for his collaboration on the initial work on hydrogen donor abilities of silicon hydrides during the late 1980s. Many thanks to Fluka Chemie AG for the Prize of ‘Reagent of the Year 1990’. The discovery of tris(trimethylsilyl)silane as a good radical-based reducing agent stimulated our research during the 1990s. I am grateful to the colleagues who have worked with me over these years on this subject for the privilege of their collaboration and friendship. I am especially grateful to Carla Ferreri for her longstanding collaboration during these years as well as her continuing support and encouragement for completing this book. Finally, I thank Hanns Fischer, Philippe Renaud, Vitaliy I. Timokhin and Andreas A. Zavitsas, for having critically read some of the chapters and for their valuable suggestions.
Page 1 and 2: Organosilanes in Radical Chemistry
Page 3 and 4: DEDICATION To my parents XrZstoB an
Page 5 and 6: viii Contents 3.6 Hydrogen Atom: An
Page 7: PREFACE A large number of papers de
Page 11 and 12: 2 Formation and Structures of Silyl
Page 19 and 20: 10 Formation and Structures of Sily
Page 27 and 28: 2 Thermochemistry 2.1 GENERAL CONSI
Page 29 and 30: Bond Dissociation Enthalpies 21 Tab
Page 31 and 32: Bond Dissociation Enthalpies 23 2.2
Page 33 and 34: Ion Thermochemistry 25 Table 2.4 Re
Page 35 and 36: Ion Thermochemistry 27 Table 2.5 El
Page 37 and 38: References 29 3. Goumri, A., Yuan,
Page 39 and 40: 32 Hydrogen Donor Abilities of Sili
Page 55 and 56: 4 Reducing Agents 4.1 GENERAL ASPEC
Page 57 and 58: General Aspects of Radical Chain Re
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Tris(trimethylsilyl)silane 53 Therm
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Tris(trimethylsilyl)silane 55 4.3.1
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Tris(trimethylsilyl)silane 57 A goo
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Tris(trimethylsilyl)silane 59 C(O)C
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Tris(trimethylsilyl)silane 61 radic
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Tris(trimethylsilyl)silane 63 86% y
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Tris(trimethylsilyl)silane 65 RO RO
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Tris(trimethylsilyl)silane 67 O AcO
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Tris(trimethylsilyl)silane 69 Tris(
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Other Silicon Hydrides 71 The reduc
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Other Silicon Hydrides 73 The decre
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Other Silicon Hydrides 75 Ph MeS O
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Other Silicon Hydrides 77 Table 4.6
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Silicon Hydride / Thiol Mixture 79
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Silylated Cyclohexadienes 81 and (4
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References 83 34. Kawashima, E., Uc
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References 85 104. Gimisis, T., Bal
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88 Addition to Unsaturated Bonds te
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90 Addition to Unsaturated Bonds ap
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92 Addition to Unsaturated Bonds 5.
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94 Addition to Unsaturated Bonds R
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96 Addition to Unsaturated Bonds Ph
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98 Addition to Unsaturated Bonds EP
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100 Addition to Unsaturated Bonds 5
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102 Addition to Unsaturated Bonds T
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104 Addition to Unsaturated Bonds R
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106 Addition to Unsaturated Bonds a
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110 Addition to Unsaturated Bonds S
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112 Addition to Unsaturated Bonds T
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114 Addition to Unsaturated Bonds I
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120 Unimolecular Reactions 1 Si(H)M
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122 Unimolecular Reactions t-Bu t-B
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124 Unimolecular Reactions MeO Si O
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126 Unimolecular Reactions t-Bu t-B
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128 Unimolecular Reactions R 1 R 2
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130 Unimolecular Reactions From the
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132 Unimolecular Reactions rearrang
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134 Unimolecular Reactions H 3 C +
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136 Unimolecular Reactions Br O Si(
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138 Unimolecular Reactions R3Si C C
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140 Unimolecular Reactions Me3Si O
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142 Unimolecular Reactions 43. Albe
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144 Consecutive Radical Reactions c
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146 Consecutive Radical Reactions O
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148 Consecutive Radical Reactions a
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150 Consecutive Radical Reactions d
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152 Consecutive Radical Reactions T
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154 Consecutive Radical Reactions M
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156 Consecutive Radical Reactions F
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162 Consecutive Radical Reactions i
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164 Consecutive Radical Reactions A
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168 Consecutive Radical Reactions r
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170 Consecutive Radical Reactions E
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174 Consecutive Radical Reactions A
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176 Consecutive Radical Reactions P
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178 Consecutive Radical Reactions f
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182 Consecutive Radical Reactions 1
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184 Consecutive Radical Reactions 8
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186 Silyl Radicals in Polymers and
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220 List of Abbreviations PED photo
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222 Index Carbonyl sulfide 111 Carb
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224 Index Organosilicon boranes 2,
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226 Index Triethylsilane as mediato
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