LEADER 05230nam 22006254a 450 001 9910829802503321 005 20230617031339.0 010 $a1-280-26956-1 010 $a9786610269563 010 $a0-470-09425-7 010 $a0-470-02475-5 035 $a(CKB)1000000000019115 035 $a(EBL)175032 035 $a(OCoLC)475880136 035 $a(SSID)ssj0000216326 035 $a(PQKBManifestationID)11221083 035 $a(PQKBTitleCode)TC0000216326 035 $a(PQKBWorkID)10197274 035 $a(PQKB)11156059 035 $a(MiAaPQ)EBC175032 035 $a(EXLCZ)991000000000019115 100 $a20030723d2004 uy 0 101 0 $aeng 135 $aur|n|---||||| 181 $ctxt 182 $cc 183 $acr 200 10$aOrganosilanes in radical chemistry$b[electronic resource] /$fChryssostomos Chatgilialoglu 210 $aWest Sussex, England $cWiley$dc2004 215 $a1 online resource (241 p.) 300 $aDescription based upon print version of record. 311 $a0-471-49870-X 320 $aIncludes bibliographical references and index. 327 $aOrganosilanes 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 327 $a2.3 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 327 $a4.1 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 327 $a4.8 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 327 $a6.1 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 327 $a7.4 Formation of Carbon-Heteroatom Bonds 330 $aIn 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 606 $aOrganosilicon compounds 606 $aFree radicals (Chemistry) 615 0$aOrganosilicon compounds. 615 0$aFree radicals (Chemistry) 676 $a547 676 $a547.08 676 $a547/.08 700 $aChatgilialoglu$b Chryssostomos$01311974 801 0$bMiAaPQ 801 1$bMiAaPQ 801 2$bMiAaPQ 906 $aBOOK 912 $a9910829802503321 996 $aOrganosilanes in radical chemistry$94112923 997 $aUNINA