Chryssostomos Chatgilialoglu

Organosilanes in Radical Chemistry (eBook, PDF)

• Format: PDF

Produktbeschreibung

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.

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Produktdetails

• Verlag: John Wiley & Sons
• Seitenzahl: 240
• Erscheinungstermin: 17. Februar 2004
• Englisch
• ISBN-13: 9780470094259
• Artikelnr.: 38185505

Autorenporträt

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.

Inhaltsangabe

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 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 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 References.
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.
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 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.
7.6 Allylations.
7.7 Application to Tandem and Cascade Radical Reactions.
7.8 References.
8 Silyl Radicals in Polymers and Materials.
8.1 Polysilanes.
8.1.1 Poly(hydrosilane)s and Related Silyl Radicals.
8.2 Oxidation Studies on Silyl-substituted Silicon Hydrides.
8.2.1 Poly(hydrosilane)s.
8.2.2 (Me3Si)3SiH and (Me3Si)2Si(H)Me as Model Compounds.
8.3 Functionalization of Poly(hydrosilane)s.
8.3.1 Halogenation.
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.
8.6 References.
List of Abbreviations.
Subject Index.

Rezensionen

"...dense with useful information...well written and easyto read..." (Applied Organometallic Chemistry, vol 19 No 1,January 2005)

"...well referenced, well produced and contains anabundance of useful examples...a welcome addition to anylibrary..." (Chemistry World, November 2004)

"...effectively blows aside the entropic fog of fuzzysuperficiality and opens a new vista of pure knowledge..."(Chemistry & Industry, 25 June 2004)

"...interesting examples and applications oforganosilanes...recommended to all researchers working in thefield..." (www.organische-chemie.ch, 25 Mar 2004)

"The scientist who already works in the field will find thisvolume to be an excellent primary source of information. It shouldalso be very useful to those teaching graduate-level courses ininorganic chemistry..." (Journal of the American ChemicalSociety, January 26, 2004)

"...an impressive work that will find favour with experiencedusers and newcomers alike...informative and stimulating...deservesspecial praise..." (Jnl of Organic Process Res and Dev,2004)