Silyl radicals have thoroughly penetrated areas as diverse as organic synthesis and material sciences, and this book surveys the most exciting aspects of their chemistry.
Focusing on silyl radicals in the liquid phase, but including gas–phase data where appropriate, topics covered include:
- methods of formation, structural characteristics and thermodynamic data
- factors governing the reactivity of silicon hydrides
- the use of silicon hydrides as radical–based reducing agents and as mediators for consecutive radical reactions
- unimolecular reactions involving silyl radicals
- silyl radicals in polymers and materials
- radical–based functionalization of hydrogen t erminated silicon surfaces
Essential reading for anyone working in free radical and/or silicon chemistry, this book will also be of interest to organic, polymer and industrial chemists as well as for those who want to approach these fields for the first time.
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.
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.
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.
4 Reducing Agents.
4.1 General Aspects of Radical Chain Reactions.
4.1.1 Radical Radical Reactions.
4.2 Radical Initiators.
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.
4.4 Other Silicon Hydrides.
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.
4.7 Silylated Cyclohexadienes.
5 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.
6 Unimolecular Reactions.
6.1 Cyclization Reactions of Silyl Radicals.
6.1.1 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.
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.
7.5 Other Useful Radical Rearrangements.
7.7 Application to Tandem and Cascade Radical Reactions.
8 Silyl Radicals in Polymers and Materials.
8.1.1 Poly(hydrosilane)s and Related Silyl Radicals.
8.2 Oxidation Studies on Silyl–substituted Silicon Hydrides.
8.2.2 (Me3Si)3SiH and (Me3Si)2Si(H)Me as Model Compounds.
8.3 Functionalization of Poly(hydrosilane)s.
8.3.2 Addition of Unsaturated Compounds.
8.3.3 Other Useful Radical Reactions.
8.4 Silylated Fullerenes.
8.5 Radical Chemistry on Silicon Surfaces.
8.5.1 Oxidation of Hydrogen–terminated Silicon Surfaces.
8.5.2 Halogenation of HwSi(111).
8.5.3 Addition of Unsaturated Compounds on HwSi(111).
8.5.4 Addition of Alkenes on Si(100) Surfaces.
8.5.5 Some Examples of Tailored Experiments on Monolayers.
List of Abbreviations.