Organosilanes in Radical Chemistry

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 ofradical 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/orsilicon chemistry as well as for those who want to approach these fields for the first time.

Autorentext

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-centred radicals have played an important role in organic synthesis, polymer chemistry and material sciences. This book offers, 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. 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.

Inhalt
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 UVVisible 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 RadicalRadical 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 (BartonMcCombie 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.

5 Addition to Unsaturated Bonds.

5.1 CarbonCarbon Double Bonds.

5.1.1 Formation of Silyl Radical Adducts.

5.1.2 Hydrosilylation of Alkenes.

5.2 CarbonCarbon Triple Bonds.

5.2.1 Formation of Silyl Radical Adducts.

5.2.2 Hydrosilylation of Alkynes.

5.3 CarbonOxygen 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 CarbonHeteroatom Multiple Bonds.

5.5 Cumulenes and Hetero-Cumulenes.

5.6 HeteroatomHeteroatom Multiple Bonds.

5.7 References.

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.

6.6 References.

7 Consecutive Radical Reactions.

7.1 Basic Concepts of CarbonCarbon Bond Formation.

7.2 Intermolecular Formation of CarbonCarbon Bonds.

7.3 Intramolecular Formation of CarbonCarbon 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 CarbonHeteroatom Bonds.

7.5 Other Useful Radical Rearrangements.

7.6 Allylations.

7.7 Application to Tandem and Cascade Radical Reactions.

7.8 References.

8 Silyl Radicals in Polymers and Materials. 8.1 Polysilanes.&lt...