Carbon-Centered Free Radicals and Radical Cations (eBook, PDF)

Structure, Reactivity, and Dynamics
Redaktion: Forbes, Malcolm D.

• Format: PDF

Produktbeschreibung

Covers the most advanced computational and experimental methods for studying carbon-centered radical intermediates With its focus on the chemistry of carbon-centered radicals and radical cations, this book helps readers fully exploit the synthetic utility of these intermediates in order to prepare fine chemicals and pharmaceutical products. Moreover, it helps readers better understand their role in complex atmospheric reactions and biological systems. Thoroughly up to date, the book highlights the most advanced computational and experimental methods available for studying and using these critically important intermediates. Carbon-Centered Free Radicals and Radical Cations begins with a short history of the field of free radical chemistry, and then covers: * A discussion of the relevant theory * Mechanistic chemistry, with an emphasis on synthetic utility * Molecular structure and mechanism, focusing on computational methods * Spectroscopic investigations of radical structure and kinetics, including demonstrations of spin chemistry techniques such as CIDNP and magnetic field effects * Free radical chemistry in macromolecules Each chapter, written by one or more leading experts, explains difficult concepts clearly and concisely, with references to facilitate further investigation of individual topics. The authors were selected in order to provide insight into a broad range of topics, including small molecule synthesis, polymer degradation, computational chemistry as well as highly detailed experimental work in the solid, liquid, and gaseous states. This volume is essential for students or researchers interested in building their understanding of the role of carbon-centered radical intermediates in complex systems and how they may be used to develop a broad range of useful products.

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Produktdetails

• Verlag: John Wiley & Sons
• Seitenzahl: 300
• Erscheinungstermin: 3. Februar 2010
• Englisch
• ISBN-13: 9780470584101
• Artikelnr.: 37297660

Autorenporträt

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.

Inhaltsangabe

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 Elliott, and Ulrich E. Steiner). 10.1
Introduction. 10.2 EPR for the Isolated Ions. 10.3 Calculation Methods for
EPR of the Isolated Ions. 10.4 Implications for Spin-Relaxation in Linked
Radical Pairs. 11. Reaction Dynamics of Carbon-Centered Radicals in Extreme
Environments Studied by the Crossed Molecular Beam Technique (Ralf I.
Kaiser). 11.1 Introduction. 11.2 The Crossed Molecular Beam Method. 11.3
Experimental Setup. 11.4 Crossed Beam Studies. 11.5 Conclusions. 12. Laser
Flash Photolysis of Photoinitiators: ESR, Optical, and IR Spectroscopy
Detection of Transients (Igor V. Khudyakov and Nicholas J. Turro). 12.1
Introduction. 12.2 Photodissociation of Initiators. 12.3 TR ESR Detection
of Transients. 12.4 Optical Detection of Transients. 12.5 IR Detection of
Free Radicals and Monitoring Their Reactions. 12.6 Concluding Remarks. 13.
Dynamics of Radical Pair Processes in Bulk Polymers (Carlos A. Chesta and
Richard G. Weiss). 13.1 Introduction. 13.2 Singlet-State Radical Pairs from
Irradiation of Aryl Esters and Alkyl Aryl Ethers. 13.2.1 General
Mechanistic Considerations From Solution and Gas-Phase Studies. 13.3
Photo-Reactions of Aryl Esters in Polymer Matrices. Kinetic Information
from Constant Intensity Irradiations. 13.4 Rate Information from Constant
Intensity Irradiation of Alkyl Aryl Ethers. 13.5 Comparison of Calculated
Rates to Other Methods for Polyethylene Films. 13.6 Triplet-State Radical
Pairs. 13.7 Concluding Remarks. 14. Acrylic Polymer Radicals: Structural
Characterization and Dynamics (Malcolm D. E. Forbes and Natalia V.
Lebedeva). 14.1 Introduction. 14.2 The Photodegradation Mechanism. 14.3
Polymer Structures. 14.4 The Time-Resolved EPR Experiment. 14.5 Tacticity
and Temperature Dependence of Acrylate Radicals. 14.6 Structural
Dependence. 14.7 Oxo-Acyl Radicals. 14.8 Spin Polarization Mechanisms. 14.9
Solvent Effects. 14.10 Dynamic Effects. 14.11 Conclusions. Index.