Stable radicals fundamentals and applied aspects of odd-electron compounds

"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 r...

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Other Authors: Hicks, Robin
Format: Book
Language:English
Published: Hoboken, N.J. Wiley 2010.
Subjects:
Radicals (Chemistry) > Stability.
Electron mobility.
Online Access:View in OPAC
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Table of Contents:
  • Machine generated contents note: <h2>Contents</h2>
  • 1. Triarylmethyl and Related Radicals
  • Thomas T. Tidwell
  • 1.1 Introduction
  • 1.2 Free radical rearrangements
  • 1.3 Other routes to triphenylmethyl radicals
  • 1.4 The persistent radical effect
  • 1.5 Properties of triphenylmethyl radicals
  • 1.6 Steric effects and persistent radicals
  • 1.7 Substituted triphenylmethyl radicals and dimers
  • 1.8 Tri(heteroaryl)methyl and related triarylmethyl radicals and dimers
  • 1.9 Delocalized persistent radicals: analogues of triarylmethyl radicals
  • 1.10 Tetrathiatriarylmethyl (TAM) radicals
  • 1.11 Perchlorinated triarylmethyl radicals
  • 1.12 Other triarylmethyl radicals
  • 1.13 Diradicals and polyradicals related to triphenylmethyl
  • 1.14 Outlook
  • References
  • 2. Polychlorotriphenylmethyl Radicals: Towards Multifunctional Molecular Materials
  • Jaume Veciana and Imma Ratera
  • 2.1 Introduction to Polychlorotriphenylmethyl Radicals
  • 2.2 Functional Molecular Materials based on PTM Radicals
  • 2.3 Multifunctional Switchable Molecular Materials based on PTM Radicals
  • 2.4 Summary
  • 2.5 References
  • 3. Phenalenyls, Cyclopentadienyls, and Other Carbon-Centered Radicals
  • Yasushi Morita and Shinsuke Nishida
  • 3.1 Introduction
  • 3.2 Open-shell graphene
  • 3.3 Phenalenyl
  • 3.4 2,5,8-Tri-tert-butylphenalenyl radical
  • 3.5 Perchlorophenalenyl radical
  • 3.6 Dithiophenalenyl radicals
  • 3.7 Nitrogen-containing phenalenyl systems
  • 3.8 Oxophenalenoxyl systems
  • 3.9 Phenalenyl-based zwitterionic radicals
  • 3.10 p-Extended phenalenyl systems
  • 3.11　Curve-structured phenalenyl system
  • 3.12 Non-alternant stable radicals
  • 3.13 Stable triplet carbenes
  • 3.14 Conclusion
  • Acknowledgement
  • References
  • 4. The Nitrogen Oxides: Persistent Radicals and van der Waals Complex Dimers
  • D. Scott Bohle
  • 4.1 Introduction
  • 4.2 Synthetic access
  • 4.3 Physical properties
  • 4.4 Structural chemistry of the monomers and dimers
  • 4.5 Electronic structure of the nitrogen oxides
  • 4.6 Reactivity of NO and NO2 and their van der Waals complexes.
  • 4.7 The kinetics of NO's termolecular reactions
  • 4.8 Biochemical and organic reactions of nitric oxide
  • 4.9 General reactivity patterns
  • 4.10 The colored species problem in NO chemistry
  • 4.11 Conclusions
  • References
  • 5. Nitroxide Radicals: Properties, Synthesis and Applications
  • Hakim Karoui, François Le Moigne, Olivier Ouari and Paul Tordo
  • 5.1 Introduction
  • 5.2 Nitroxide structure
  • 5.3 Nitroxide Multiradicals
  • 5.4 Nitronyl Nitroxides (NNOs)
  • 5.5 Synthesis of Nitroxides
  • 5.6 Chemical properties of nitroxides
  • 5.7 Nitroxides in supramolecular entities
  • 5.8 Nitroxides for Dynamic Nuclear Polarization (DNP) Enhanced NMR
  • 5.9 Nitroxides as pH-sensitive spin probes
  • 5.10 Nitroxides as prefluorescent probes
  • 5.11 Approaches to Improve the Resistance of Nitroxides toward Bioreduction
  • 5.12 EPR-Spin Trapping Technique
  • 5.13 Conclusions
  • References
  • 6. The Only Stable Organic Sigma Radicals: Di-tert-Alkyliminoxyls
  • Keith U. Ingold
  • 6.1 Introduction
  • 6.2 The Discovery of Stable Iminoxyls
  • 6.3 Hydrogen Atom Abstraction by Di-tert-Butyliminoxyl
  • 6.4 Other Reactions and Non-Reactions of Di-tert-Butyliminoxyl
  • 6.5 Di-tert-Alkyliminoxyls More Sterically Crowded Than Di-tert-Butyliminoxyl
  • 6.6 Di-(1-Adamantyl)iminoxyl. A Truly Stable -Radical
  • References
  • 7. Verdazyls and Related Radicals Containing the Hydrazyl [R2N-NR] Group
  • Robin G. Hicks
  • 7.1 Introduction
  • 7.2 Verdazyl radicals
  • 7.3 Tetraazapentenyl radicals
  • 7.4 Tetrazolinyl radicals
  • 7.5 1,2,4-Triazolinyl radicals
  • 7.6 1,2,4,5-Tetrazinyl radicals
  • 7.7 Benzo-1,2,4-triazinyl radicals
  • 7.8 Summary
  • References
  • 8.Metal Coordinated Phenoxyl Radicals
  • Prof. Fabrice Thomas
  • 8.1 Introduction
  • 8.2 General properties of phenoxyl radicals
  • 8.3 Occurrence of tyrosyl radicals in proteins
  • 8.4 Complexes with coordinated phenoxyl radicals
  • 8.5 Conclusions
  • 8.6 Abbreviations
  • Notes and References
  • 9. The Synthesis and Characterization of Stable Radicals Containing the Thiazyl (SN) Fragment and their use as Building Blocks for Advanced Functional Materials
  • Robin G. Hicks
  • 9.1 Introduction
  • 9.2 Radicals based exclusively on sulfur and nitrogen
  • 9.3 "Organothiazyl" radicals
  • 9.4 Thiazyl radicals as "advanced materials"
  • 9.5 Summary
  • References
  • 10. Stable Radicals of the Heavy p-block Elements
  • Jari Konu and Tristram Chivers
  • 10.1 Introduction
  • 10.2 Group 13 Element Radicals
  • 10.3 Group 14 Element Radicals
  • 10.4 Group 15 Element Radicals
  • 10.5 Group 16 Element Radicals
  • 10.6 Group 17 Element Radicals
  • 10.7 Summary and Future Prospects
  • References
  • 11. Application of Stable Radicals as Mediators in Living-Radical Polymerization
  • Andrea R. Szkurhan, Julie Lukkarila and Michael K. Georges
  • 11.1 Introduction
  • 11.2 Living Polymerizations
  • 11.3 Stable Free Radical Polymerization
  • 11.4 Non-Nitroxide-Based Radicals as Mediating Agents
  • 11.5 Aqueous Stable Free Radical Polymerization Processes
  • 11.6 The Application of Stable Free Radical Polymerization to New Materials
  • 11.7 Conclusions
  • References
  • 12. Nitroxide-Catalyzed Alcohol Oxidations In Organic Synthesis
  • Christian Bruckner
  • 12.1 Introduction
  • 12.2 Mechanism of TEMPO-catalyzed Alcohol Oxidations
  • 12.3 Nitroxides Used as Catalysts
  • 12.4 Chemoselectivity: Oxidation of Primary vs. Secondary Alcohols
  • 12.5 Chemoselectivity: Oxidation of Primary vs. Benzylic Alcohols
  • 12.6 Oxidation of Secondary Alcohols to Ketones
  • 12.7 Oxidation of Alcohols to Carboxylic Acids
  • 12.8 Stereoselective Nitroxide-catalyzed Oxidations
  • 12.9 Secondary Oxidants Used in Nitroxide-catalyzed Reactions
  • 12.10 Use of Nitroxide-catalyzed Oxidations in Tandem Reactions
  • 12.11 Predictable Side Reactions
  • 12.12 Comparison with Other Oxidation Methods
  • 12.13 Reflections on Nitroxide-catalyzed Oxidations and Green Chemistry
  • Acknowledgements
  • References
  • 13. Metal-nitroxide complexes: synthesis and magneto-structural correlations
  • Victor Ovcharenko
  • 12.1 Introduction
  • 12.2 Two types of nitroxide for direct coordination of the metal to the nitroxyl group
  • 12.3 Ferro- and ferrimagnets based on metal-nitroxide complexes
  • 12.4 Heterospin systems based on polynuclear compounds of metals with nitroxides
  • 12.5 Breathing crystals
  • 12.6 Other studies of metal-nitroxides
  • 12.7 Conclusions
  • 12.8 References
  • 14. Rechargeable Batteries Using Robust But Redox-Active Organic Radicals
  • Takeo Suga and Hiroyuki Nishide
  • 14.1 Introduction
  • 14.2 Redox Reaction of Organic Radicals
  • 14.3 Mechanism and Performance of Organic Radical Battery
  • 14.4 Molecular Design and Synthesis of Redox-active Radical Polymers
  • 14.5 A Totally Organic-based Radical Battery
  • 14.6 Conclusion and Future Prospects
  • 14.7 References
  • 15. Spin Labeling: A Modern Perspective
  • Lawrence J. Berliner
  • 15.1 Introduction
  • 15.2 The early years
  • 15.3 Advantages of nitroxides
  • 15.4 Applications of spin labeling to biochemical and biological systems.
  • 15.5 Distance measurements
  • 15.6 Site directed spin labeling (SDSL): how is it done?
  • 15.7 Other spin labeling applications
  • 15.8 Synopsis
  • References
  • 16. Functional In Vivo EPR Spectroscopy and Imaging Using Nitroxide and Trityl Radicals
  • Valery V. Khramtsov and Jay L. Zweier
  • 16.1 Introduction
  • 16.2 Nitroxyl radicals
  • 16.3 Triarylmethyl (trityl) radicals
  • 16.4 In vivo EPR oximetry using nitroxyl and trityl probes
  • 16.5 EPR spectroscopy and imaging of pH using nitroxyl and trityl probes
  • 16.6 Redox- and thiol-sensitive nitroxide probes
  • 16.7 Conclusions
  • Acknowledgments
  • References
  • 17. Biologically Relevant Chemistry of Nitroxides
  • Sara Goldstein and Amram Samuni
  • 17.1 Introduction
  • 17.2 Mechanisms of nitroxide reactions with biologically relevant small radicals
  • 17.3 Nitroxides as SOD-mimics
  • 17.4 Nitroxides as catalytic antioxidants in biological systems
  • 17.5 Conclusions
  • References.

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