Organosilanes in radical chemistry [[electronic resource] /] / Chryssostomos Chatgilialoglu

• Record Nr.: UNINA9910146249703321
• Autore: Chatgilialoglu Chryssostomos
• Pubbl/distr/stampa: West Sussex, England, : Wiley, c2004
• ISBN: 1-280-26956-1; 9786610269563; 0-470-09425-7; 0-470-02475-5
• Descrizione fisica: 1 online resource (241 p.)
• Disciplina: 547; 547.08; 547/.08
• Soggetti: Organosilicon compounds; Free radicals (Chemistry); Electronic books.
• Lingua di pubblicazione: Inglese
• Formato: Materiale a stampa
• Livello bibliografico: Monografia
• Note generali: Description based upon print version of record.
• Nota di bibliografia: Includes bibliographical references and index.
• Nota di contenuto: Organosilanes in Radical Chemistry; CONTENTS; 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 Thermochemistry2.3.1 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 Reactions4.1.1 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 References5 Addition to Unsaturated Bonds; 5.1 Carbon-Carbon Double Bonds; 5.1.1 Formation of Silyl Radical Adducts; 5.1.2 Hydrosilylation of Alkenes; 5.2 Carbon-Carbon Triple Bonds; 5.2.1 Formation of Silyl Radical Adducts; 5.2.2 Hydrosilylation of Alkynes; 5.3 Carbon-Oxygen Double Bonds; 5.3.1 Formation of Silyl Radical Adducts; 5.3.2 Hydrosilylation of Carbonyl Groups; 5.3.3 Radical Brook Rearrangement; 5.4 Other Carbon-Heteroatom Multiple Bonds; 5.5 Cumulenes and Hetero-Cumulenes; 5.6 Heteroatom-Heteroatom Multiple Bonds; 5.7 References; 6 Unimolecular Reactions; 6.1 Cyclization Reactions of Silyl Radicals6.1.1 Five-membered Ring Expansion; 6.2 Aryl Migration; 6.3 Acyloxy Migration; 6.4 Intramolecular Homolytic Substitution at Silicon; 6.5 Homolytic Organosilicon Group Transfer; 6.6 References; 7 Consecutive Radical Reactions; 7.1 Basic Concepts of Carbon-Carbon Bond Formation; 7.2 Intermolecular Formation of Carbon-Carbon Bonds; 7.3 Intramolecular Formation of Carbon-Carbon Bonds (Cyclizations); 7.3.1 Construction of Carbocycles; 7.3.2 Construction of Cyclic Ethers and Lactones; 7.3.3 Construction of Cyclic Amines and Lactames; 7.4 Formation of Carbon-Heteroatom Bonds
• Sommario/riassunto: 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 togetherExcellent reference tool for experienced practitioners of radical and/or silicon chemistryPresents various aspects of the