UID:
almafu_9960161353902883
Format:
1 online resource (758 pages)
ISBN:
9780128019917
,
0128019913
Note:
Includes index.
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Front Cover -- Organosilicon Compounds -- Copyright Page -- Contents -- List of Contributors -- About the Author -- Preface -- I. Theory -- 1 Nonclassical Organosilicon Compounds -- 1.0 Abbreviations -- 1.1 Pyramidal Structures -- 1.2 Sandwich Compounds -- 1.3 Hypercoordination and Hypervalency -- 1.4 Silicon Analogs of Triangulenes -- Acknowledgments -- References -- II. Experiment -- 1 Synthesis -- 1.1 Organosilicon Compounds of Tetracoordinate Silicon -- 2 Transition Metal Complexes of Silicon (Excluding Silylene Complexes) -- 2.1 Introduction -- 2.2 Late Transition Metal Complexes -- 2.3 Early Transition Metal Complexes -- 2.4 Conclusions -- References -- 3 Organosilicon Clusters -- 3.1 Introduction -- 3.2 Synthesis -- 3.2.1 General Synthetic Methods: Si-Si Bond Formation -- 3.2.1.1 Wurtz-type coupling of halosilanes with metals -- 3.2.1.2 Coupling of halosilanes with silyl anions -- 3.2.1.3 Rearrangement of oligosilanes with aluminum chloride -- 3.2.1.4 Oxidative coupling of silyl anion -- 3.2.1.5 Dehydrogenative coupling of hydrosilanes with transition metal catalysts -- 3.2.2 Early Work -- 3.2.3 Cage Compounds -- 3.2.3.1 Bicyclo[1.1.1]pentasilanes and persilastaffanes -- 3.2.3.2 Bicyclo[2.2.1]heptasilanes and bicyclo[2.2.2]octasilanes -- 3.2.3.3 Bicyclo[3.3.1]nonasilanes and bicyclo[4.3.1]decasilane -- 3.2.3.4 Tricyclo[2.1.0.02,5]pentasilanes -- 3.2.3.5 Tricyclo[2.2.0.02,5]hexasilanes -- 3.2.3.6 Heptasilanortricyclene -- 3.2.3.7 Decasilaadamantane -- 3.2.3.8 Tetracyclo[3.3.0.02,7.03,6]octasilanes -- 3.2.4 Polyhedranes -- 3.2.4.1 Tetrasilatetrahedranes and bi(tetrasilatetrahedranyl) -- 3.2.4.2 Hexasilaprismanes -- 3.2.4.3 Octasilacubanes -- 3.2.5 Ring Catenation Compounds -- 3.2.5.1 Bicyclo[1.1.0]tetrasilanes -- 3.2.5.2 Tricyclo[3.1.0.02,4]hexasilane -- 3.2.5.3 Tetracyclo[3.3.0.01,3.05,7]octasilane.
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3.2.5.4 Pentacyclo[5.1.0.01,6.02,5.03,5]octasilane -- 3.2.5.5 Ladder oligosilanes51 -- 3.2.5.6 Tricyclo[5.3.0.02,6]decasilane -- 3.2.5.7 Bicyclo[3.3.0]octasilanes, bicyclo[4.2.0]octasilanes, and bicyclo[4.3.0]nonasilane -- 3.2.5.8 Bicyclo[4.4.0]decasilane -- 3.2.5.9 Bicyclo[1.1.0]tetrasil-1(2)-ene and bicyclo[3.3.0]octasil-1(5)-ene: organosilicon clusters with a Si=Si double bond -- 3.2.6 Spirooligosilanes -- 3.2.7 Siliconoids: Organosilicon Clusters Containing Unsubstituted Silicon Atoms -- 3.2.7.1 Si8 cluster -- 3.2.7.2 Pentasila[1.1.1]propellane -- 3.2.7.3 Tricyclo[2.1.0.01,3]pentasilane -- 3.2.7.4 Isomers of hexasilabenzene -- 3.2.8 Control of Oligomerization by the Ring Size of Cyclooligosilane Precursors -- 3.3 Structural Analysis by X-ray Crystallography and Temperature-Dependent 1H NMR Spectroscopy -- 3.3.1 Bond-Stretch Isomers and Molecular Dynamics of Bicyclo[1.1.0]tetrasilanes -- 3.3.2 Bridgehead Si-Si Bonds of Pentasila[1.1.1]propellane and Related Compounds -- 3.3.3 Trigonal Monopyramidal and Inverted Tetrahedral Structures of Silicon Atoms -- 3.3.3.1 Trigonal monopyramidal structures -- 3.3.3.2 Inverted tetrahedral structures -- 3.3.4 Tricyclic Isomer of Hexasilabenzene -- 3.4 Structural Analysis by 29Si NMR Spectroscopy -- 3.4.1 29Si INEPT-INADEQUATE NMR Spectroscopy -- 3.4.2 2D 29Si/1H Correlation NMR Spectroscopy -- 3.4.3 Solid State 29Si CP-MAS NMR Spectroscopy -- 3.4.4 Unusual Downfield Shifts of 29Si NMR Signals -- 3.4.4.1 Ring current effect -- 3.4.4.2 Charge distribution effect -- 3.4.4.3 Steric compression effect -- 3.4.4.4 Consideration of the Ramsay's equation -- 3.5 Electronic Properties -- 3.5.1 Fundamentals of Molecular Orbitals of Organosilicon Clusters -- 3.5.2 Recent Topics -- 3.5.2.1 Spiropentasiladiene -- 3.5.2.2 Pentasila[1.1.1]propellane and a hexasilabenzene isomer with a global minimum energy.
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3.5.2.3 Persilastaffanes -- 3.6 Reactions -- 3.6.1 Si-Si Bond Cleavage -- 3.6.2 Rearrangement of Silicon Skeletons -- 3.6.3 Isomerization -- 3.6.4 Unique Reactivity of Siliconoids -- 3.6.5 Oxidation -- 3.6.6 Photochemical Reactions -- 3.7 Ionic Organosilicon Clusters -- 3.7.1 Anions -- 3.7.2 Radical Anions -- 3.7.3 Cations -- 3.8 Conclusions -- References -- 4 Chiral Organosilicon Compounds -- 4.1 Introduction -- 4.2 Synthesis of Chiral Organosilicon Compounds -- 4.2.1 Optical Resolution or Kinetic Resolution -- 4.2.2 Desymmetrization of Functional Organosilicon Compounds With Chiral Reagents -- 4.2.3 Asymmetric Catalysis: Enzymatic Method -- 4.2.4 Transition Metal-Catalyzed Synthesis of Silicon-Stereogenic Silanes -- 4.2.5 Other Synthetic Methods by Transformation of Chiral Organosilicon Compounds -- 4.3 The Application of Chiral Organosilicon Compounds -- 4.4 Summary -- References -- 1.2 Organosilicon Compounds of Low-Coordinate Silicon -- 5 Silicon-Centered Cations -- 5.0 List of Abbreviations -- 5.1 Introduction -- 5.2 Synthesis of Silylium Ions R3Si+ -- 5.2.1 From Silyl Hydrides R3Si-H -- 5.2.2 From Silanes R3Si-CR3 -- 5.2.3 From Disilanes R3Si-SiR3 -- 5.2.4 From Silyl Halides R3Si-X -- 5.2.5 From Low-Coordinate Organosilicon Derivatives -- 5.2.5.1 From silylenes R2Si -- 5.2.5.2 From silyl radicals R3Si -- 5.3 Structural Assessment of Silylium Ions -- 5.3.1 29Si NMR Spectroscopy -- 5.3.2 X-ray Crystallography -- 5.4 Stable Silylium Ions -- 5.4.1 Inter- and Intramolecularly Stabilized Silylium Ions -- 5.4.1.1 Oxidation of the Si-H bond -- 5.4.1.2 Oxidation of the Si-C bond -- 5.4.1.3 Other methods -- 5.4.2 "Free" Silylium Ions -- 5.4.2.1 Trigonal-planar silylium ions -- 5.4.2.2 Delocalized silylium ions -- 5.5 Application of Silylium Ions in Organic Synthesis -- 5.5.1 Diels-Alder Reactions -- 5.5.2 Friedel-Crafts Reactions.
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5.5.3 Hydrodefluorination Reactions -- 5.5.4 Activation of Small Molecules (CO2, H2) -- 5.5.5 Hydrosilylation Reactions -- 5.5.6 Miscellaneous Reactions of Silylium Ions -- 5.6 Summary -- References -- 6 Silicon-Centered Radicals -- 6.1 Introduction -- 6.2 Fundamentals of EPR Spectroscopy -- 6.2.1 Principles and Spectroscopy Techniques -- 6.2.1.1 The EPR spectrometer -- 6.2.2 Line Width -- 6.2.3 Line Shape -- 6.2.4 Hyperfine Coupling -- 6.2.5 EPR of Triplet Biradicals -- 6.2.6 Simulation of EPR Spectra -- 6.3 Silyl Radicals-General Introduction -- 6.3.1 Controlling the Stability of Silyl Radicals -- 6.3.1.1 Thermodynamic stability-electronic effects -- 6.3.1.2 Kinetic stabilization-steric effects -- 6.3.2 Structure -- 6.3.3 EPR Spectra of Silyl Radicals -- 6.4 Silyl Substituted Silyl Radicals -- 6.4.1 Mono-Silyl Substituted Silyl Radical -- 6.4.2 Bis(Silyl)-Substituted Silyl Radicals -- 6.4.2.1 H(R3Si)2Si -- 6.4.2.2 R′(R3Si)2Si (R′=aryl) -- 6.4.2.3 Amino-substituted silyl radical -- 6.5 Tris(Silyl)-Substituted Silyl Radicals -- 6.5.1 EPR Parameters -- 6.5.2 X-ray Crystallography -- 6.5.3 Reactions -- 6.5.3.1 Dimerization -- 6.5.3.2 Photochemistry -- 6.5.3.3 Oxidation, reduction, and ionization -- 6.5.4 Silyl Radicals in Batteries -- 6.5.5 Conformational Analysis of Stable Silyl Radicals in Solution -- 6.6 Silicon-Centered Bi- and Triradicals -- 6.6.1 Triplet Silyl Biradical -- 6.6.2 Si-Centered Triradical -- 6.6.3 Thermally Accessible Triplet State of the Highly Twisted Tetrakis(di-tert-butylmethylsilyl)disilene -- 6.7 Silicon-Centered Anion-Radicals -- 6.7.1 Reduction of Multiply-Bonded Silicon-Compounds -- 6.7.1.1 Disilenes -- 6.7.1.2 Disilynes -- 6.7.1.3 Phosphasilene -- 6.7.1.4 Radical-anions of silanone -- 6.7.2 Reduction of Silylenes -- 6.7.3 Alkali Metal- and Mercury-Substituted Silyl Radicals -- 6.7.3.1 Aggregated silyllithium radicals.
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6.7.3.2 Hg-substituted silyl radicals -- 6.8 Transition Metal Substututed Silyl Radicals -- 6.9 Conclusions -- Acknowledgments -- References -- 7 Silicon-Centered Anions -- 7.0 List of Abbreviations -- 7.1 Introduction -- 7.2 General Synthetic Methods for the Preparation of Silyl Anions -- 7.3 Synthesis of Different Silyl Anions -- 7.3.1 Alkylated Silyl Anions -- 7.3.2 Arylated Silyl Anions -- 7.3.3 Chiral Silyl Anions -- 7.3.4 Oligosilanyl Anions -- 7.3.4.1 Cyclic oligosilanyl anions -- 7.3.4.2 Polycyclic and cage type oligosilanyl anions -- 7.3.5 Functionalized Anions -- 7.3.5.1 Hydrogen substituted anions -- 7.3.5.2 Halogen substituted anions -- 7.3.5.3 N-substituted anions -- 7.3.5.4 O- and S-substituted anions -- 7.3.5.5 Other functionalized anions -- 7.3.6 Silyl Dianions -- 7.3.6.1 Geminal silyl dianions -- 7.3.6.2 Vicinal dianions -- 7.3.6.3 1,3-Dianions -- 7.3.6.4 1,4-Dianions -- 7.3.6.5 Dianions with longer spacer units -- 7.3.6.6 Bridged dianions -- 7.3.7 Delocalized Silyl Anions -- 7.3.8 Sila-Enolates -- 7.3.9 Silenyl and Disilenyl Anions -- 7.3.10 Hypercoordinate Anions (Silicates) -- 7.3.10.1 Zwitterionic silicates -- 7.3.10.2 Pentaorganosilicates -- 7.3.10.3 Hydridosilicates -- 7.4 Conclusion and Outlook -- References -- 8 Stable Silylenes and Their Transition Metal Complexes -- 8.0 List of Abbreviations -- 8.1 Introduction -- 8.2 Cyclic Diaminosilylenes -- 8.2.1 Synthesis and Molecular Structures -- 8.2.2 Reactions With Haloalkanes and Halosilanes -- 8.2.3 Transition Metal Complexes and Related Metal Species of Stable Cyclic Diaminosilylenes -- 8.2.3.1 Group 1 metals -- 8.2.3.2 Group 2 metals -- 8.2.3.3 Group 6 metals -- 8.2.3.4 Group 8 metals -- 8.2.3.5 Group 9 metals -- 8.2.3.6 Group 10 metals -- 8.2.3.7 Group 11 metals -- 8.2.3.8 Group 12 metals -- 8.2.3.9 Other metals -- 8.2.4 Other Reactions.
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8.3 Diaminosilylenes Derived From β-Diketiminate.
Additional Edition:
ISBN 9780128019818
Additional Edition:
ISBN 0128019816
Language:
English
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