Ion-Radical Organic Chemistry: Principles and Applications, Second Edition, 2nd Edition (Hardback) book cover

Ion-Radical Organic Chemistry

Principles and Applications, Second Edition, 2nd Edition

By Zory Vlad Todres

CRC Press

496 pages | 365 B/W Illus.

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Consolidating knowledge from a number of disciplines, Ion-Radical Organic Chemistry: Principles and Applications, Second Edition presents the recent changes that have occurred in the field since the publication of the first edition in 2003.

This volume examines the formation, transformation, and application of ion-radicals in typical conditions of organic synthesis. Avoiding complex mathematics, the author explains the principles of ion-radical organic chemistry and presents an overview of organic ion-radical reactions. He reviews methods of determining ion-radical mechanisms and controlling ion-radical reactions. Wherever applicable, the text addresses issues relating to ecology and biomedical concerns as well as inorganic participants of the ion-radical organic reactions.

After reviewing the nature of organic ion-radicals and their ground-state electronic structure, the book discusses their formation, the relationship between electronic structure and reactivity, mechanism and regulation of reactions, stereochemical aspects, synthetic opportunities, and practical applications. Additional topics include electronic and opto-electronic devices, organic magnets and conductors, lubricants, other materials, and reactions of industrial or biomedical importance.

The book concludes by providing an outlook on possible future development in this field. Researchers and practitioners engaged in active work on synthetic or mechanistic organic chemistry and its practical applications will find this text to be invaluable in both its scope and its depth.


"The author offers broad yet deeply detailed coverage… This book will be a useful resource for specialists already versed in aspects of ion-radical chemistry as well for those seeking a survey of the primary literature as a foundation to begin research in the area… I would recommend it as an addition to the monograph collections of chemical research libraries."

Journal of the American Chemical Society, 2009, 131 (6)

Table of Contents

Nature of Organic Ion-Radicals and Their Ground-State Electronic Structure


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-Radical Basicity 

Pathways of Hydrogen Detachment from Anion-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



Formation of Organic Ion-Radicals


Chemical Methods of Organic Ion-Radical Preparation



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 



Electronic Structure–Reactivity Relationship in Ion-Radical Organic Chemistry 


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 



Discerning Mechanism of Ion-Radical Organic Reactions


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 


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)2

System of NaNO2 and CF3SO3

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



Regulating Ion-Radical Organic Reactions


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 


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 



Stereochemical Aspects of Ion-Radical Organic Reactions 


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 



Synthetic Opportunities of Ion-Radical Organic Chemistry


Reductive and Oxidative Reactions

Transformation of Ethylenic Ion-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 


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 



Ion-Radical Organic Chemistry in Its Practical Applicability


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


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 



General Outlook 

Importance of Ion-Radical Organic Chemistry 

Scientometric Notes 




Subject Categories

BISAC Subject Codes/Headings:
MEDICAL / Biochemistry
SCIENCE / Chemistry / Organic
SCIENCE / Chemistry / Physical & Theoretical