Stable Radicals : Fundamentals and Applied Aspects of Odd-Electron Compounds

by
Format: eBook
Pub. Date: 2010-07-01
Publisher(s): Wiley
Availability: This title is currently not available.
List Price: $195.00

Rent Textbook

Select for Price
There was a problem. Please try again later.

New Textbook

We're Sorry
Sold Out

Used Textbook

We're Sorry
Sold Out

eTextbook

We're Sorry
Not Available

Summary

Stable radicals - molecules with odd electrons which are sufficiently long lived to be studied or isolated using conventional techniques - have enjoyed a long history and are of current interest for a broad array of fundamental and applied reasons, for example to study and drive novel chemical reactions, in the development of rechargeable batteries or the study of free radical reactions in the body.In Stable Radicals: Fundamentals and Applied Aspects of Odd-Electron Compounds a team of international experts provide a broad-based overview of stable radicals, from the fundamental aspects of specific classes of stable neutral radicals to their wide range of applications including synthesis, materials science and chemical biology. Topics covered include: triphenylmethyl and related radicals polychlorinated triphenylmethyl radicals: towards multifunctional molecular materials phenalenyls, cyclopentadienyls, and other carbon-centered radicals the nitrogen oxides: persistent radicals and van der Waals complex dimers nitroxide radicals: properties, synthesis and applications the only stable organic sigma radicals: di-tert-alkyliminoxyls. delocalized radicals containing the hydrazyl [R2N-NR] unit metal-coordinated phenoxyl radicals stable radicals containing the thiazyl unit: synthesis, chemical, and materials properties stable radicals of the heavy p-block elements application of stable radicals as mediators in living-radical polymerization nitroxide-catalyzed alcohol oxidations in organic synthesis metal-nitroxide complexes: synthesis and magneto-structural correlations rechargeable batteries using robust but redox-active organic radicals spin labeling: a modern perspective functional in vivo EPR spectroscopy and imaging using nitroxides and trityl radicals biologically relevant chemistry of nitroxidesStable Free Radicals: Fundamentals and Applied Aspects of Odd-Electron Compounds is an essential guide to this fascinating area of chemistry for researchers and students working in organic and physical chemistry and materials science.

Table of Contents

Preface
List of Contributors
Triarylmethyl and Related Radicals
Introduction
Free radical rearrangements
Other routes to triphenylmethyl radicals
The persistent radical effect
Properties of triphenylmethyl radicals
Steric effects and persistent radicals
Substituted triphenylmethyl radicals and dimers
Tris(heteroaryl)methyl and related triarylmethyl radicals
Delocalized persistent radicals: analogues of triarylmethyl radicals
Tetrathiatriarylmethyl (TAM) and related triarylmethyl radicals
Perchlorinated triarylmethyl radicals
Other triarylmethyl radicals
Diradicals and polyradicals related to triphenylmethyl
Outlook
Acknowledgements
References
Polychlorotriphenylmethyl Radicals: Towards Multifunctional Molecular Materials
Introduction
Functional molecular materials based on PTM radicals
Multifunctional switchable molecular materials based on PTM radicals
Conclusions
Phenalenyls, Cyclopentadienyls, and Other Carbon-Centered Radicals
Introduction
Open shell graphene
Phenalenyl
2,5,8-Tri- tert -butylphenalenyl radical
Perchlorophenalenyl radical
Dithiophenalenyl radicals
Nitrogen-containing phenalenyl systems
Oxophenalenoxyl systems
Phenalenyl-based zwitterionic radicals
¿ -Extended phenalenyl systems
Curve-structured phenalenyl system
Non-alternant stable radicals
Stable triplet carbenes
Conclusions
The Nitrogen Oxides: Persistent Radicals and van der Waals Complex Dimers
Introduction
Synthetic access
Physical properties
Structural chemistry of the monomers and dimers
Electronic structure of nitrogen oxides
Reactivity of nitric oxide and nitrogen dioxide and their van der Waals complexes
The kinetics of nitric oxide's termolecular reactions
Biochemical and organic reactions of nitric oxide
General reactivity patterns
The colored species problem in nitric oxide chemistry
Conclusions
Nitroxide Radicals: Properties, Synthesis and Applications
Introduction
Nitroxide structure
Nitroxide multiradicals
Nitronyl nitroxides (NNOs)
Synthesis of nitroxides
Chemical properties of nitroxides
Nitroxides in supramolecular entities
Nitroxides for dynamic nuclear polarization (DNP) enhanced NMR
Nitroxides as pH-sensitive spin probes
Nitroxides as prefluorescent probes
EPR-spin trapping technique
Conclusions
The Only Stable Organic Sigma Radicals: Di- tert -Alkyliminoxyls
Introduction
The discovery of stable iminoxyls
Hydrogen atom abstraction by di- tert -butyliminoxyl
Other reactions and non-reactions of di- tert -butyliminoxyl
Di- tert -alkyliminoxyls more sterically crowded than di- tert -butyliminoxyl
Di-(1-Adamantyl)iminoxyl: a truly stable ¿ radical
Verdazyls and Related Radicals Containing the Hydrazyl [R2N−NR] Group
Introduction
Verdazyl radicals
Tetraazapentenyl radicals
Tetrazolinyl radicals
1,2,4-Triazolinyl radicals
1,2,4,5-Tetrazinyl radicals
Benzo-1,2,4-triazinyl radicals
Summary
Metal Coordinated Phenoxyl Radicals
Introduction
General properties of phenoxyl radicals
Occurrence of tyrosyl radicals in proteins
Complexes with coordinated phenoxyl radicals
Conclusions
Abbreviations
The Synthesis and Characterization of Stable Radicals Containing the Thiazyl (SN) Fragment and Their Use as Building Blocks for Advanced Functional Materials
Introduction
Radicals based exclusively on sulfur and nitrogen
"Organothiazyl" radicals
Thiazyl radicals as "advanced materials"
Conclusions
Stable Radicals of the Heavy p-Block Elements
Introduction
Group 13 element radicals
Group 14 element radicals
Group 15 element radicals
Group 16 element radicals
Group 17 element radicals
Summary and future prospects
Application of Stable Radicals as Mediators in Living-Radical Polymerization
Introduction
Living polymerizations
Stable free radical polymerization
Triazolinyl radicals
Aqueous stable free radical polymerization processes
The application of stable free radical polymerization to new materials
Conclusions
List of abbreviations
Nitroxide-Catalyzed Alcohol Oxidations in Organic Synthesis
Introduction
Mechanism of TEMPO-catalyzed alcohol oxidations
Nitroxides used as catalysts
Chemoselectivity: oxidation of primary vs secondary alcohols
Chemoselectivity: oxidation of primary vs benzylic alcohols
Oxidation of secondary alcohols to ketones
Oxidations of alcohols to carboxylic acids
Stereoselective nitroxide-catalyzed oxidations
Secondary oxidants used in nitroxide-catalyzed reactions
Use of nitroxide-catalyzed oxidations in tandem reactions
Predictable side reactions
Comparison with other oxidation methods
Nitroxide-catalyzed oxidations and green chemistry
Metal-Nitroxide Complexes: Synthesis and Magnetostructural Correlations
Introduction
Two types of nitroxide for direct coordination of the metal to the nitroxyl group
Ferro- and ferrimagnets based on metal-nitroxide complexes
Heterospin systems based on polynuclear compounds of metals with nitroxides
Breathing crystals
Other studies of metal-nitroxides
Conclusions
Rechargeable Batteries Using Robust but Redox Active Organic Radicals
Introduction
Redox reaction of organic radicals
Mechanism and performance of an organic radical battery
Molecular design and synthesis of redox active radical polymers
A totally organic-based radical battery
Conclusions
Spin Labeling: A Modern Perspective
Introduction
The early years
Advantages of nitroxides
Applications of spin labeling to biochemical and biological systems
Distance measurements
Site directed spin labeling (SDSL): how is it done?
Other spin labeling applications
Conclusions
Functional in vivo EPR Spectroscopy and Imaging Using Nitroxide and Trityl Radicals
Introduction
Nitroxyl radicals
Triarylmethyl (trityl) radicals
In vivo EPR oximetry using nitroxyl and trityl probes
EPR spectroscopy and imaging of pH using nitroxyl and trityl probes
Redox- and thiol-sensitive nitroxide probes
Conclusions
Biologically Relevant Chemistry of Nitroxides
Introduction
Mechanisms of nitroxide reactions with biologically relevant small radicals
Nitroxides as SOD mimics
Nitroxides as catalytic antioxidants in biological systems
Conclusions
Acknowledgements
References
Index
Table of Contents provided by Publisher. All Rights Reserved.

An electronic version of this book is available through VitalSource.

This book is viewable on PC, Mac, iPhone, iPad, iPod Touch, and most smartphones.

By purchasing, you will be able to view this book online, as well as download it, for the chosen number of days.

Digital License

You are licensing a digital product for a set duration. Durations are set forth in the product description, with "Lifetime" typically meaning five (5) years of online access and permanent download to a supported device. All licenses are non-transferable.

More details can be found here.

A downloadable version of this book is available through the eCampus Reader or compatible Adobe readers.

Applications are available on iOS, Android, PC, Mac, and Windows Mobile platforms.

Please view the compatibility matrix prior to purchase.