Ion-Radical Organic Chemistry : Principles and Applications

Nature of Organic Ion-Radicals and Their Ground-State Electronic Structure Introduction Unusual Features Substituent Effects Connections between Ion-Radical Reactivity and Electronic Structure of Ion-Radical Products Bridge-Effect Peculiarities Acid-Base Properties of Organic Ion-Radicals Anion-Radicals Anion-Radical Basicity Pathways of Hydrogen Detachment from Anion-Radicals Cation-Radicals Cation-Radical Acidity Cation-Radical Basicity Cation-Radicals as Acceptors or Donors of Hydrogen Atoms Metallocomplex Ion-Radicals Metallocomplex Anion-Radicals Metallocomplex Cation-Radicals Bridge Effect in Metallocomplex Ion-Radicals Charge-Transfer Coordination to Metallocomplex Ion-Radicals Organic Ion-Radicals with Several Unpaired Electrons or Charges Polymeric Ion-Radicals Inorganic Ion-Radicals in Reactions with Organic Substrates Superoxide Ion Reactions of Superoxide Ion with Organic H Acids Reactions of Superoxide Ion with Organic Electrophiles Superoxide Ion in Reactions with Biological Objects Superoxide Ion-Ozone Anion-Radical Relation Atomic Oxygen Anion-Radical Molecular Oxygen Cation-Radical Carbon Dioxide Anion-Radical Carbonate Radical Sulfur Dioxide Anion-Radical Sulfite Radical Sulfate Radical Hydroxide Anion Nitrosonium and Nitronium Ions Tris(aryl)amine and Thianthrene Cation-Radicals Trialkyloxonium Hexachloroantimonates Transition Metal Ions Conclusion References Formation of Organic Ion-Radicals Introduction Chemical Methods of Organic Ion-Radical Preparation Anion-Radicals Cation-Radicals Carbenoid Ion-Radicals Equilibria in Liquid-Phase Electron-Transfer Reactions Electrochemical Methods versus Chemical Methods Charge-Transfer Phenomena Template Effects Adsorption Phenomena Stereochemical Phenomena Concentration Effects on the Fate of Ion-Radicals at Electrodes and in Solutions Aggregation of Ion-Radical Salts Direct Influence on Electron-Transfer Equilibrium Electron-Transfer Reactions with Participation of Ion-Radical Aggregates Kinetic and Mechanistic Differences between Electrode and Chemical (Homogeneous) Ion-Radical Dimerization Formation of Organic Ion-Radicals in Living Organisms Isotope-Containing Organic Compounds as Ion-Radical Precursors Kinetic Isotope Effects in Electron-Transfer Reactions Behavior of Isotope Mixtures in Electron-Transfer Reactions Organic Ion-Radicals in Solid Phases Organic Ion-Radicals in Frozen Solutions Organic Ion-Radical as Constituents of Solid Salts Formation and Behavior of Ion-Radicals within Confines Micellar Media Porous Media Capsule Media Conclusion References Electronic Structure-Reactivity Relationship in Ion-Radical Organic Chemistry Introduction Principle of "Detained" Electron That Controls Ion-Radical Reactivity Frontier-Orbital Control Steric Control over Spin Delocalization Unpaired Electron Localization in the Field of Two or More Atoms Spin-Charge Separation (Distonic Stabilization of Ion-Radicals) Distonic Stabilization of Anion-Radicals Distonic Stabilization of Cation-Radicals Ion-Pair Formation Detention of Unpaired Electron in a Framework of One Specific Molecular Fragment Formation of Closed Contour for Unpaired Electron Delocalization Principle of "Released" Electron that Controls Ion-Radical Reactivity Effects of Spread Conjugation in Ion-Radicals Derived from Molecules with Large Contours of Delocalization Spin Delocalization in Ion-Radicals Derived from Molecules of Increased Dimensionality Biomedical Aspects of Ion-Radical Organic Chemistry Cation-Radical Damage in Deoxyribonucleic Acid Ionization Potentials of Carcinogens Localization of Charges and Spins in Cation-Radicals of Carcinogens On Geometrical and Spatial Factors Governing the Behavior of Ion-Radicals in Biological Systems Ion-Radical Repair of Damaged Deoxyribonucleic Acid Cation-Radical Intermediates in Metabolism of Furan Xenobiotics Behavior of Anion-Radicals in Living Organisms Conclusion References Discerning Mechanism of Ion-Radical Organic Reactions Introduction Why Do Reactions Choose Ion-Radical Mechanism? Chemical Approaches to Identification of Ion-Radical Organic Reactions Identification According to Structure of Final Products Identification According to Correlation within Reaction Series Identification According to Disturbance of "Leaving-Group Strength" Correlation Kinetic Approaches to Identification of Ion-Radical Reactions Kinetic Isotope Effect Other Kinetic Approaches Positional Reactivity and Distribution of Spin Density in Substrate Ion-Radicals Identification by Methods of Chemical Probes Initiation of Polymerization of Vinyl Additives Method of Inhibitors Method of Radical and Spin Traps Physical Approaches to Identification of Ion-Radical Reactions Radiospectroscopy Electron Spin Resonance Methods Nuclear Magnetic Resonance Methods Optical Spectroscopy Methods Electron Spectroscopy Vibration Spectroscopy Other Physical Methods Magnetic Susceptibility Mass Spectrometry Electrochemical Modeling of Ion-Radical Reactions X-Ray Diffraction Examples of Complex Approaches to Discernment of Ion-Radical Mechanism of Organic Reactions Oxidative Polymerization of Anilines Reactions of Hydroperoxides with Phosphites and Sulfides Ter Meer Reaction Aromatic Nitration System of HNO3 and H2SO4 with Catalytic Amounts of HNO2 System of HNO3 and (CH3CO)2O System of NaNO2 and CF3SO3H Systems of Metal Nitrites with Oxidizers Systems of Metal Nitrates with Oxidizers Systems with Tetranitromethane as Nitrating Agent Systems with Participation of Nitrogen Dioxide Nitration and Hydroxylation by Peroxynitrite Gas-Phase Nitration Meerwein and Sandmeyer Reactions Conclusion References Regulating Ion-Radical Organic Reactions Introduction Physical Effects Effect of Light Effect of Electric Field Effect of Magnetic Field Effect of Microwave Field Effect of Acoustic Field Effect of Mechanical Action Mechanochromism Mechanopolymerization and Mechanolysis Effect of Chemical Additives Solvent Effects Static Effects General Solvation Selective Solvation and Solute-Solvent Binding Dynamic Effects Solvent Reorganization Solvent Polarity and Polarization Solvent Internal Pressure Solvent Conformational Transition Solvent Temperature Liquid Crystals and Ionic Liquids as Solvents Salt Effects Salt Effect on Spin Density Distribution Salt-Cage Effect Interplay Salt Effect on Course of Ion-Radical Reactions Conclusion References Stereochemical Aspects of Ion-Radical Organic Reactions Introduction Problem of Steric Restrictions Reflection of the Ion-Radical Step in Reaction Steric Results Conformational Transition of Ion-Radicals Space Structure and Skeletal Isomerization of Ion-Radicals Conclusion References Synthetic Opportunities of Ion-Radical Organic Chemistry Introduction Reductive and Oxidative Reactions Transformation of Ethylenic Ion-Radicals Anion-Radicals Cation-Radicals Reduction of Ketones into Alcohols Preparation of Dihydroaromatics Synthetic Suitability of (Dialkylamino)benzene Cation-Radicals Ion-Radical Polymerization Anion-Radical Polymerization Cation-Radical Polymerization Formation of Linear Main Chains Formation of Cyclic and Branched Chains Ring Closure Cation-Radical Ring Closure H-Acid Catalysis Cation-Radical Mechanism Anion-Radical Ring Closure Ring Closure Involving Cation- and Anion-Radicals in Linked Molecular Systems Ring Opening Fragmentation Selective Oxidation Selective Oxidation of Alkylbenzenes Selective Oxidation of Dimethylimidazole Cation-Radical Route to Group Deprotection Removal of Butoxycarbonyl Protective Group Removal of Methoxybenzyl Protective Group Removal of Trimethylsilyl Protective Group Scission of Carbon-Carbon Bonds Synthon-Influential Bond Scission Bond Formation Opportunities Associated with SRN1 Reactions Substrate Structure Nature of Introducing Groups Reaction Medium Dark SRN1 Reactions Conclusion References Ion-Radical Organic Chemistry in Its Practical Applicability Introduction Organic Ion-Radicals in Microelectronics Ion-radical Approach to Molecular Switches and Modulators Cation-Radicals of Triarylamines in Optical-Recording Media Ladder Polymerization of Fluoranthene-Based Cation-Radicals as Route to Electrochromic Materials Organic Metals Semiconductors Organic Magnets Lubrication in Terms of Ion-Radical Organic Chemistry Ion-Radical Organic Chemistry in Its Contributions to Wood Delignification and Fossil-Fuel Desulfurization Paper Fabrication Manufacture of Commercial Products from Delignification Wastes Desulfurization of Fossil Fuels Conclusion References General Outlook Importance of Ion-Radical Organic Chemistry Scientometric Notes Prospects References Index