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Informationen zum Autor MALCOLM D. E. FORBES, PhD, is Professor of Chemistry at the University of North Carolina at Chapel Hill, where he has served in various capacities since 1990. Professor Forbes's group is involved in free radical research and electron paramagnetic resonance spectroscopy. He is a renowned educator and lecturer and has received numerous awards for his research and teaching methods, including the Sir Harold Thomson Award from Elsevier, a Japan Society for the Promotion of Science Foreign Fellowship Award, a National Science Foundation Young Investigator Award, and the Bernard Smaller Prize for Research in Magnetic Resonance. In 2008, he was a J. W. Fulbright Senior Scholar, living and working in Novosibirsk, Russia. Klappentext The chemistry and biochemistry of reactive intermediates is central to modern mechanistic and quantitative understanding of organic chemistry and biochemistry. The only comprehensive review to cover carbon-centered radical intermediates and their role(s) in chemistry and biochemistry, Carbon-Centered Radicals provides detailed explanations of the role of these intermediates in organic reactions and detailed discussions of their versatility with respect to functional groups to help graduate students and professional researchers better understand and expand their synthetic utility. Zusammenfassung * The chemistry and biochemistry of reactive intermediates iscentral to modern mechanistic and quantitative understanding oforganic chemistry and biochemistry. Inhaltsverzeichnis About the Volume Editor. Preface to Series. Introduction. Contributors. 1. A Brief History of Carbon Radicals (Malcolm D. E. Forbes). 2. Intermolecular Radical Additions to Alkynes: Cascade-Type Radical Cyclizations (Uta Wille). 2.1 Introduction. 2.2 Cascade Reactions Involving Radicals of Second Row Elements. 2.3 Cascade Reactions Initiated by Addition of Higher Main Group (VI)-Centered Radicals to Alkynes. 2.4 Cascade Reactions Initiated by Addition of Higher Main Group (VI)-Centered Radicals to Alkynes. 2.5 Cascade Reactions Initiated by Addition of Higher Main Group (V)-Centered Radicals to Alkynes. 3. Radical Cation Fragmentation Reactions in Organic Synthesis (Alexander J. Poniatowski and Paul E. Floreancig). 3.1 Introduction. 3.2 Electron Transfer-Initiated Cyclization Reactions. 3.3 Oxidative Acyliminium Ion Formation. 3.4 Carbon-Carbon Bond Formation. 3.5 Summary and Outlook. 4. Selectivity in Radical Cation Cycloadditions (Christo S. Sevov and Olaf Wiest). 4.1 Introduction. 4.2 Mechanism and the Origin of the Rate Acceleration. 4.3 Selectivity in Radical Cation Cycloadditions. 4.4 Chemoselectivity. 4.5 Regioselectivity. 4.6 Periselectivity. 4.7 Endo/Exo Selectivity. 4.8 Conclusions. 5. The Stability of Carbon-Centered Radicals (Michelle L. Coote, Ching Yeh Lin, and Hendrik Zipse). 5.1 Introduction. 5.2 Theoretical Methods. 5.3 RSE Values for Carbon-Centered Radicals. 5.4 Use of RSE Values in Practical Applications. 5.5 Conclusions. 6. Interplay of Stereoelectronic Vibrational and Environmental Effects in Tuning Physicochemical Properties of Carbon-Centered Radicals (Vincenzo Barone, Malgorzata Biczysko, and Paola Cimino). 6.1 Introduction. 6.2 EPR Spectroscopy. 6.3 Calculation of EPR Parameters. 6.4 Vibrational Properties Beyond the Harmonic Approximation. 6.5 Electronic Properties: Vertical Excitation Energies, Structure, and Frequencies in Excited Electronic States. 6.6 Vibronic Spectra. 6.7 Concluding Remarks. 7. Unusual Structures of Radical Ions in Carbon Skeletons: Nonstandard Chemical Bonding by Restricting Geometries (Georg Gesc...
List of contents
About the Volume Editor.
Preface to Series.
Introduction.
Contributors.
1. A Brief History of Carbon Radicals (Malcolm D. E. Forbes).
2. Intermolecular Radical Additions to Alkynes: Cascade-Type Radical Cyclizations (Uta Wille).
2.1 Introduction.
2.2 Cascade Reactions Involving Radicals of Second Row Elements.
2.3 Cascade Reactions Initiated by Addition of Higher Main Group (VI)-Centered Radicals to Alkynes.
2.4 Cascade Reactions Initiated by Addition of Higher Main Group (VI)-Centered Radicals to Alkynes.
2.5 Cascade Reactions Initiated by Addition of Higher Main Group (V)-Centered Radicals to Alkynes.
3. Radical Cation Fragmentation Reactions in Organic Synthesis (Alexander J. Poniatowski and Paul E. Floreancig).
3.1 Introduction.
3.2 Electron Transfer-Initiated Cyclization Reactions.
3.3 Oxidative Acyliminium Ion Formation.
3.4 Carbon-Carbon Bond Formation.
3.5 Summary and Outlook.
4. Selectivity in Radical Cation Cycloadditions (Christo S. Sevov and Olaf Wiest).
4.1 Introduction.
4.2 Mechanism and the Origin of the Rate Acceleration.
4.3 Selectivity in Radical Cation Cycloadditions.
4.4 Chemoselectivity.
4.5 Regioselectivity.
4.6 Periselectivity.
4.7 Endo/Exo Selectivity.
4.8 Conclusions.
5. The Stability of Carbon-Centered Radicals (Michelle L. Coote, Ching Yeh Lin, and Hendrik Zipse).
5.1 Introduction.
5.2 Theoretical Methods.
5.3 RSE Values for Carbon-Centered Radicals.
5.4 Use of RSE Values in Practical Applications.
5.5 Conclusions.
6. Interplay of Stereoelectronic Vibrational and Environmental Effects in Tuning Physicochemical Properties of Carbon-Centered Radicals (Vincenzo Barone, Malgorzata Biczysko, and Paola Cimino).
6.1 Introduction.
6.2 EPR Spectroscopy.
6.3 Calculation of EPR Parameters.
6.4 Vibrational Properties Beyond the Harmonic Approximation.
6.5 Electronic Properties: Vertical Excitation Energies, Structure, and Frequencies in Excited Electronic States.
6.6 Vibronic Spectra.
6.7 Concluding Remarks.
7. Unusual Structures of Radical Ions in Carbon Skeletons: Nonstandard Chemical Bonding by Restricting Geometries (Georg Gescheidt).
7.1 Introduction.
7.2 The Tools.
7.3 Pagodane and Its Derivatives.
7.4 Different Stages of Cycloaddition/Cycloreversion Reactions Within Confined Environments.
7.5 Extending the ''Cage Concept''.
7.6 Summary.
8. Magnetic Field Effects on Radical Pairs in Homogeneous Solution (Jonathan. R. Woodward).
8.1 Introduction.
8.2 The Spin-Correlated Radical Pair.
8.3 Application of a Magnetic Field.
8.4 Spin-State Mixing.
8.5 The Magnetic Field Dependence of Radical Pair Reactions.
8.6 Theoretical Approaches.
8.7 Experimental Approaches.
8.8 The Life Cycle of Radical Pairs in Homogeneous Solution.
8.9 Summary.
9. Chemical Transformations Within the Paramagnetic World Investigated by Photo-CIDNP (Martin Goez).
9.1 Introduction.
9.2 CIDNP Theory.
9.3 Experimental Methods.
9.4 Radical--Radical Transformations During Diffusive Excursions.
9.5 Radical--Radical Transformations at Reencounters.
9.6 Interconversions of Biradicals.
9.7 Conclusions.
10. Spin Relaxation in Ru-Chromophore-Linked Azine/Diquat Radical Pairs (Matthew T. Rawls, Ilya Kuprov, C. Michael E
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"Overall this volume is relevant to both students and accomplished researchers alike and is highly recommended. The price is certainly affordable." (Journal of the American Chemical Society, November 2010)
