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Informationen zum Autor Chryssostomos Chatgilialoglu is Research Director at the Italian National Research Council - CNR - in Bologna, President and cofounder of the spin-off company Lipinutragen and Chairman of the COST Action CM1201 on Biomimetic Radical Chemistry - 2013-2016 . He received the doctorate degree in Industrial Chemistry from Bologna University in 1976 and completed his postdoctoral studies at York University - UK - and the National Research Council of Canada, Ottawa. From March 2014 to May 2016 he was appointed as the Director of the Institute of Nanoscience and Nanotechnology at the NCSR "Demokritos" in Athens. Klappentext 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. Zusammenfassung Silicon-centered radicals play an important role in organic synthesis! polymer chemistry and material sciences. This book offers a description of silyl radicals within an interdisciplinary context! connecting structural characteristics and chemical properties to their application in different areas of chemistry. Inhaltsverzeichnis Preface. Acknowledgements. 1 Formation and Structures of Silyl Radicals. 1.1 Methods of Generation of Silyl Radicals. 1.2 Structural Properties of Silyl Radicals. 1.2.1 Chemical Studies. 1.2.2 Electron Paramagnetic Resonance (EPR) Spectra. 1.2.3 Crystal Structures. 1.2.4 UV-Visible Spectra. 1.2.5 Theoretical Studies. 1.3 References. 2 Thermochemistry. 2.1 General Considerations. 2.2 Bond Dissociation Enthalpies. 2.2.1 Radical Kinetics. 2.2.2 Photoacoustic Calorimetry. 2.2.3 Theoretical Data. 2.2.4 Derived Bond Dissociation Energies. 2.3 Ion Thermochemistry. 2.3.1 Negative-ion Cycles. 2.3.2 Hydride-affinity Cycles. 2.4 References. 3 Hydrogen Donor Abilities of Silicon Hydrides. 3.1 Carbon-centred Radicals. 3.1.1 Primary Alkyl Radicals and Free-Radical Clock Methodology. 3.1.2 Other Types of Carbon-centred Radicals. 3.2 Nitrogen-centred Radicals. 3.3 Oxygen-centred Radicals. 3.3.1 Alkoxyl Radicals. 3.3.2 Peroxyl Radicals. 3.3.3 Aryloxyl and Aroyloxyl Radicals. 3.4 Sulfur-centred Radicals. 3.5 Ketone Triplets. 3.6 Hydrogen Atom: An Example of Gas-phase Kinetics. 3.7 Theoretical Approaches. 3.8 References. 4 Reducing Agents. 4.1 General Aspects of Radical Chain Reactions. 4.1.1 Radical-Radical Reactions. 4.2 Radical Initiators. 4.3 Tris(trimethylsilyl)silane. 4.3.1 Dehalogenations. 4.3.2 Reductive Removal of Chalcogen Groups (RS and RSe). 4.3.3 Deoxygenation of Alcohols (Barton-McCombie Reaction). 4.3.4 Miscellaneous Reactions. 4.3.5 Appendix. 4.4 Other Silicon Hydrides. 4.4.1 Trialkylsilanes. 4.4.2 Phenyl Substituted Silicon Hydrides. 4.4.3 Silyl Substituted Silicon Hydrides. 4.4.4 Alkylthio Substituted Silicon Hydrides. 4.5 Silicon Hydride/Thiol Mixture. 4.6 Silanethiols. 4.7 Silylated Cyclohexadienes. 4.8 References. ...
