Radical Ions.

Concern rating on recent developments of radical ion chemistry, this book discusses radical ions not only as relatively stable aromatic systems that can exist in solution, but as transition metal complexes, and as unstable organic and inorganic species that are stabilized in liquids. Complementary aspects of radical ions in solids and in solution have been stressed. This discussion comprehensively examines generation, identification, spin density determination, and reactivity of radical ions. GENERATION – in addition to the conventional methods of generation by chemical reduction and oxidation in solution and by electrochemical means, several chapters describe how gamma radiation can be used to produce new types of radical ions. IDENTIFICATION – although it has largely been performed by EPR, it is shown that official methods are often useful for identification. The power of optical techniques is discussed for organic and inorganic systems SPIN DENSITY DETERMINATION – determination from experimental data and the concomitant testing of molecular orbital theory has been of major importance. The present situation is summarized for organic and inorganic systems. REACTIVITY – a new and exciting area. Generation of new radical ions by utilizing their reactivity is discussed; the complex equilibria which are found for ketyl radical ions are examined; and an outline of radical ion chemistry involving selective electron and positive ion transfer in the organic solid state is developed. 1. Electron Spin Densities. James R. Bolton 1 2. Metal Ketyls and Related Radical Ions – Electronic Structures and Ion Pair Equilibria. Noboru Hirota 35 3. Semidione Radical Anions. Glen A. Russell 87 4. Radical Cations. Gershon Vincow 151 5. Orbital Degeneracy in Benzene and Substituent Effects. Kerry W. Bowers 211 6. Recent Advances in the Chemistry of Aromatic Anion Radicals. M. Thomas Jones 245 7. Some Organometallic Radicals and Ion Radicals of the Group IV Elements. Grant Urry 275 8. Radical Anions of Sulfur-Containing Aromatic Compounds. M. M. Urberg and E. T. Kaiser 301 9. Ionic Processes in γ-Irradiated Organic Solids at -196°. William H. Hamill 321 10. The Structure of Inorganic Radicals. Hilary J. Bower, M. C. R. Symons, and D. J. A. Tinling 417 11. Fragments in Irradiated Ionic Solids. Joseph Cunningham 475 12. Trapped Radicals in Inorganic Glasses. A. Treinin 525 13. Electron Spin Resonance of First Row Transition Metal Complex Ions. H. A. Kuska and Max T. Rogers 579 Author Index 747 Subject Index 785