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

Robin Hicks (Editor)
ISBN: 978-0-470-77083-2
606 pages
August 2010
Stable Radicals: Fundamentals and Applied Aspects of Odd-Electron Compounds (047077083X) cover image


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 nitroxides

Stable 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.

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Table of Contents


List of Contributors.

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 Tris(heteroaryl)methyl and related triarylmethyl radicals.

1.9 Delocalized persistent radicals: analogues of triarylmethyl radicals.

1.10 Tetrathiatriarylmethyl (TAM) and related triarylmethyl radicals.

1.11 Perchlorinated triarylmethyl radicals.

1.12 Other triarylmethyl radicals.

1.13 Diradicals and polyradicals related to triphenylmethyl.

1.14 Outlook.



2. Polychlorotriphenylmethyl Radicals: Towards Multifunctional Molecular Materials (Jaume Veciana and Imma Ratera).

2.1 Introduction.

2.2 Functional molecular materials based on PTM radicals.

2.3 Multifunctional switchable molecular materials based on PTM radicals.

2.4 Conclusions.

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 π-Extended phenalenyl systems.

3.11 Curve-structured phenalenyl system.

3.12 Non-alternant stable radicals.

3.13 Stable triplet carbenes.

3.14 Conclusions.

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 nitrogen oxides.

4.6 Reactivity of nitric oxide and nitrogen dioxide and their van der Waals complexes.

4.7 The kinetics of nitric oxide's termolecular reactions.

4.8 Biochemical and organic reactions of nitric oxide.

4.9 General reactivity patterns.

4.10 The colored species problem in nitric oxide chemistry.

4.11 Conclusions.

5. Nitroxide Radicals: Properties, Synthesis and Applications (Hakim Karoui, Franc¸ois Le Moigne, Olivier Ouari and Paul Tordoi).

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 EPR-spin trapping technique.

5.12 Conclusions.

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 σ radical.

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.

8. Metal Coordinated Phenoxyl Radicals (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.

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 Conclusions.

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.

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.

11.4.1 Triazolinyl radicals.

11.5 Aqueous stable free radical polymerization processes.

11.6 The application of stable free radical polymerization to new materials.

11.7 Conclusions.

List of abbreviations.

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 Oxidations 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 Nitroxide-catalyzed oxidations and green chemistry.

13. Metal–Nitroxide Complexes: Synthesis and Magnetostructural Correlations (Victor Ovcharenko).

13.1 Introduction.

13.2 Two types of nitroxide for direct coordination of the metal to the nitroxyl group.

13.3 Ferro- and ferrimagnets based on metal–nitroxide complexes.

13.4 Heterospin systems based on polynuclear compounds of metals with nitroxides.

13.5 Breathing crystals.

13.6 Other studies of metal–nitroxides.

13.7 Conclusions.

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 an organic radical battery.

14.4 Molecular design and synthesis of redox active radical polymers.

14.5 A totally organic-based radical battery.

14.6 Conclusions.

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 Conclusions.

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.

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.




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"This is a worthwhile and insightful anthology and leaves the reader with the impression that novel prospects and discoveries could surface at any moment from junctions on the stable radical chemical topology." (Angewandte Chemie, 2011)
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