Organic molecular compounds
CONTENTS CHAPTER NATURE OF ORGANIC ION-RADICALS AND THEIR GROUND-STATE ELECTRONIC STRUCTURE 1 1 INTRODUCTION 1 2 UNUSUAL FEATURES 1 2 1 SUBSTITUENT EFFECTS 1 2 2 CONNECTIONS BETWEEN ION-RADICAL REACTIVITY AND ELECTRONIC STRUCTURE OF ION-RADICAL PRODUCTS 1 2 3 BRIDGE-EFFECT PECULIARITIES 1 3 ACID–BASE PROPERTIES OF ORGANIC ION-RADICALS 1 3 1 ANION-RADICALS ANION-RADICAL BASICITY 1 3 1 2 PATHWAYS OF HYDROGEN DETACHMENT FROM ANION-RADICALS 1 3 2 CATION-RADICALS 1 3 2 1 CATION-RADICAL ACIDITY 1 3 2 2 CATION-RADICAL BASICITY 1 3 2 3 CATION-RADICALS AS ACCEPTORS OR DONORS OF HYDROGEN ATOMS 1 4 METALLOCOMPLEX ION-RADICALS 1 4 1 METALLOCOMPLEX ANION-RADICALS 1 4 2 METALLOCOMPLEX CATION-RADICALS 1 4 3 BRIDGE EFFECT IN METALLOCOMPLEX ION-RADICALS 1 4 4 CHARGE-TRANSFER COORDINATION TO METALLOCOMPLEX ION-RADICALS 1 5 ORGANIC ION-RADICALS WITH SEVERAL UNPAIRED ELECTRONS OR CHARGES 1 6 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 REACTIONS OF SUPEROXIDE ION 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 SUL? TE RADICAL SULFATE RADICAL HYDROXIDE ANION 1 7 10 NITROSONIUM AND NITRONIUM IONS 1 7 11 TRIS(ARYL)AMINE AND THIANTHRENE CATION-RADICALS 1 7 12 TRIALKYLOXONIUM HEXACHLOROANTIMONATES 1 7 13 TRANSITION METAL IONS 1 8 CONCLUSION REFERENCES CHAPTER FORMATION OF ORGANIC ION-RADICALS 2 1 INTRODUCTION 2 2 CHEMICAL METHODS OF ORGANIC ION-RADICAL PREPARATION 2 2 1 ANION-RADICALS 2 2 2 CATION-RADICALS 2 2 3 CARBENOID ION-RADICALS 2 3 EQUILIBRIA IN LIQUID-PHASE ELECTRON-TRANSFER REACTIONS 2 4 ELECTROCHEMICAL METHODS VERSUS CHEMICAL METHODS 2 4 1 CHARGE-TRANSFER PHENOMENA 2 4 2 TEMPLATE EFFECTS 2 4 3 ADSORPTION PHENOMENA 2 4 4 STEREOCHEMICAL PHENOMENA 2 4 5 CONCENTRATION EFFECTS ON THE FATE OF ION-RADICALS AT ELECTRODES AND IN SOLUTIONS 2 4 6 AGGREGATION OF ION-RADICAL SALTS 2 4 6 1 DIRECT IN? UENCE ON ELECTRON-TRANSFER EQUILIBRIUM 2 4 6 2 ELECTRON-TRANSFER REACTIONS WITH PARTICIPATION OF ION-RADICAL AGGREGATES 2 4 6 3 KINETIC AND MECHANISTIC DIFFERENCES BETWEEN ELECTRODE AND CHEMICAL (HOMOGENEOUS) ION-RADICAL DIMERIZATION 2 5 FORMATION OF ORGANIC ION-RADICALS IN LIVING ORGANISMS 2 6 ISOTOPE-CONTAINING ORGANIC COMPOUNDS AS ION-RADICAL PRECURSORS 2 6 1 KINETIC ISOTOPE EFFECTS IN ELECTRON-TRANSFER REACTIONS 2 6 2 BEHAVIOR OF ISOTOPE MIXTURES IN ELECTRON-TRANSFER REACTIONS 2 7 ORGANIC ION-RADICALS IN SOLID PHASES ORGANIC ION-RADICALS IN FROZEN SOLUTIONS 2 7 2 ORGANIC ION-RADICAL AS CONSTITUENTS OF SOLID SALTS 2 8 FORMATION AND BEHAVIOR OF ION-RADICALS WITHIN CON? NES 2 8 1 MICELLAR MEDIA 2 8 2 POROUS MEDIA 2 8 3 CAPSULE MEDIA 2 9 CONCLUSION ELECTRONIC STRUCTURE–REACTIVITY RELATIONSHIP IN ION-RADICAL ORGANIC CHEMISTRY 3 1 INTRODUCTION 3 2 PRINCIPLE OF “DETAINED” ELECTRON THAT CONTROLS ION-RADICAL REACTIVITY 3 2 1 FRONTIER-ORBITAL CONTROL 3 2 2 STERIC CONTROL OVER SPIN DELOCALIZATION 3 2 3 UNPAIRED ELECTRON LOCALIZATION IN THE FIELD OF TWO OR MORE ATOMS 3 2 4 SPIN–CHARGE SEPARATION (DISTONIC STABILIZATION OF ION-RADICALS) 3 2 4 1 DISTONIC STABILIZATION OF ANION-RADICALS 3 2 4 2 DISTONIC STABILIZATION OF CATION-RADICALS 3 2 5 ION-PAIR FORMATION 3 2 5 1 DETENTION OF UNPAIRED ELECTRON IN A FRAMEWORK OF ONE SPECI? C MOLECULAR FRAGMENT 3 2 5 2 FORMATION OF CLOSED CONTOUR FOR UNPAIRED ELECTRON DELOCALIZATION 3 3 PRINCIPLE OF “RELEASED” ELECTRON THAT CONTROLS ION-RADICAL REACTIVITY 3 3 1 EFFECTS OF SPREAD CONJUGATION IN ION-RADICALS DERIVED FROM MOLECULES WITH LARGE CONTOURS OF DELOCALIZATION 3 3 2 SPIN DELOCALIZATION IN ION-RADICALS DERIVED FROM MOLECULES OF INCREASED DIMENSIONALITY 3 4 BIOMEDICAL ASPECTS OF ION-RADICAL ORGANIC CHEMISTRY 3 4 1 CATION-RADICAL DAMAGE IN DEOXYRIBONUCLEIC ACID IONIZATION POTENTIALS OF CARCINOGENS 3 4 1 2 LOCALIZATION OF CHARGES AND SPINS IN CATION-RADICALS OF CARCINOGENS 3 4 2 ON GEOMETRICAL AND SPATIAL FACTORS GOVERNING THE BEHAVIOR OF ION-RADICALS IN BIOLOGICAL SYSTEMS 3 4 3 ION-RADICAL REPAIR OF DAMAGED DEOXYRIBONUCLEIC ACID 3 4 4 CATION-RADICAL INTERMEDIATES IN METABOLISM OF FURAN XENOBIOTICS 3 4 5 BEHAVIOR OF ANION-RADICALS IN LIVING ORGANISMS 3 5 CONCLUSION DISCERNING MECHANISM OF ION-RADICAL ORGANIC REACTIONS 4 1 INTRODUCTION 4 2 WHY DO REACTIONS CHOOSE ION-RADICAL MECHANISM? 4 3 CHEMICAL APPROACHES TO IDENTI? CATION OF ION-RADICAL ORGANIC REACTIONS 4 3 1 IDENTI? CATION ACCORDING TO STRUCTURE OF FINAL PRODUCTS 4 3 2 IDENTI? CATION ACCORDING TO CORRELATION WITHIN REACTION SERIES 4 3 3 IDENTI? CATION ACCORDING TO DISTURBANCE OF “LEAVING-GROUP STRENGTH” CORRELATION 4 3 4 KINETIC APPROACHES TO IDENTI? CATION OF ION-RADICAL REACTIONS 4 3 4 1 KINETIC ISOTOPE EFFECT 4 3 4 2 OTHER KINETIC APPROACHES 4 3 5 POSITIONAL REACTIVITY AND DISTRIBUTION OF SPIN DENSITY IN SUBSTRATE ION-RADICALS 4 3 6 IDENTI? CATION BY METHODS OF CHEMICAL PROBES 4 3 6 1 INITIATION OF POLYMERIZATION OF VINYL ADDITIVES 4 3 6 2 METHOD OF INHIBITORS 4 3 6 3 METHOD OF RADICAL AND SPIN TRAPS 4 4 PHYSICAL APPROACHES TO IDENTI? CATION OF ION-RADICAL REACTIONS 4 4 1 RADIOSPECTROSCOPY 4 4 1 1 ELECTRON SPIN RESONANCE METHODS 4 4 1 2 NUCLEAR MAGNETIC RESONANCE METHODS 4 4 2 OPTICAL SPECTROSCOPY METHODS 4 4 2 1 ELECTRON SPECTROSCOPY 4 4 2 2 VIBRATION SPECTROSCOPY 4 4 3 OTHER PHYSICAL METHODS 4 4 3 1 MAGNETIC SUSCEPTIBILITY 4 4 3 2 MASS SPECTROMETRY 4 4 3 3 ELECTROCHEMICAL MODELING OF ION-RADICAL REACTIONS 4 4 3 4 X-RAY DIFFRACTION 4 5 EXAMPLES OF COMPLEX APPROACHES TO DISCERNMENT OF ION-RADICAL MECHANISM OF ORGANIC REACTIONS 4 5 1 OXIDATIVE POLYMERIZATION OF ANILINES 4 5 2 REACTIONS OF HYDROPEROXIDES WITH PHOSPHITES AND SUL? DES 4 5 3 TER MEER REACTION 4 5 4 AROMATIC NITRATION 4 5 4 1 SYSTEM OF HNO3 AND H2SO4 WITH CATALYTIC AMOUNTS OF HNO2 4 5 4 2 SYSTEM OF HNO3 AND (CH3CO)2O 4 5 4 3 SYSTEM OF NANO2 AND CF3SO3H 4 5 4 4 SYSTEMS OF METAL NITRITES WITH OXIDIZERS 4 5 4 5 SYSTEMS OF METAL NITRATES WITH OXIDIZERS 4 5 4 6 SYSTEMS WITH TETRANITROMETHANE AS NITRATING AGENT 4 5 4 7 SYSTEMS WITH PARTICIPATION OF NITROGEN DIOXIDE 4 5 4 8 NITRATION AND HYDROXYLATION BY PEROXYNITRITE 4 5 4 9 GAS-PHASE NITRATION 4 5 5 MEERWEIN AND SANDMEYER REACTIONS 4 6 CONCLUSION REGULATING ION-RADICAL ORGANIC REACTIONS 5 1 INTRODUCTION 5 2 PHYSICAL EFFECTS 5 2 1 EFFECT OF LIGHT 5 2 2 EFFECT OF ELECTRIC FIELD 5 2 3 EFFECT OF MAGNETIC FIELD 5 2 4 EFFECT OF MICROWAVE FIELD 5 2 5 EFFECT OF ACOUSTIC FIELD 5 2 6 EFFECT OF MECHANICAL ACTION 5 2 6 1 MECHANOCHROMISM 5 2 6 2 MECHANOPOLYMERIZATION AND MECHANOLYSIS 5 3 EFFECT OF CHEMICAL ADDITIVES 5 4 SOLVENT EFFECTS 5 4 1 STATIC EFFECTS GENERAL SOLVATION 5 4 1 2 SELECTIVE SOLVATION AND SOLUTE-SOLVENT BINDING 5 4 2 DYNAMIC EFFECTS 5 4 2 1 SOLVENT REORGANIZATION 5 4 2 2 SOLVENT POLARITY AND POLARIZATION 5 4 2 3 SOLVENT INTERNAL PRESSURE 5 4 2 4 SOLVENT CONFORMATIONAL TRANSITION 5 4 2 5 SOLVENT TEMPERATURE 5 4 3 LIQUID CRYSTALS AND IONIC LIQUIDS AS SOLVENTS 5 5 SALT EFFECTS 5 5 1 SALT EFFECT ON SPIN DENSITY DISTRIBUTION 5 5 2 SALT-CAGE EFFECT INTERPLAY 5 5 3 SALT EFFECT ON COURSE OF ION-RADICAL REACTIONS 5 6 CONCLUSION STEREOCHEMICAL ASPECTS OF ION-RADICAL ORGANIC REACTIONS 6 1 INTRODUCTION 6 2 PROBLEM OF STERIC RESTRICTIONS 6 4 CONFORMATIONAL TRANSITION OF ION-RADICALS 6 5 SPACE STRUCTURE AND SKELETAL ISOMERIZATION OF ION-RADICALS 6 6 CONCLUSION SYNTHETIC OPPORTUNITIES OF ION-RADICAL ORGANIC CHEMISTRY INTRODUCTION 7 2 REDUCTIVE AND OXIDATIVE REACTIONS 7 2 1 TRANSFORMATION OF ETHYLENIC ION-RADICALS ANION-RADICALS 7 2 1 2 CATION-RADICALS 7 2 2 REDUCTION OF KETONES INTO ALCOHOLS 7 2 3 PREPARATION OF DIHYDROAROMATICS 7 2 4 SYNTHETIC SUITABILITY OF (DIALKYLAMINO)BENZENE CATION-RADICALS 7 3 ION-RADICAL POLYMERIZATION ANION-RADICAL POLYMERIZATION 7 3 2 CATION-RADICAL POLYMERIZATION 7 3 2 1 FORMATION OF LINEAR MAIN CHAINS 7 3 2 2 FORMATION OF CYCLIC AND BRANCHED CHAINS 7 4 RING CLOSURE CATION-RADICAL RING CLOSURE 7 4 2 ANION-RADICAL RING CLOSURE 7 4 3 RING CLOSURE INVOLVING CATION- AND ANION-RADICALS IN LINKED MOLECULAR SYSTEMS 7 5 RING OPENING 7 6 FRAGMENTATION 7 6 1 SELECTIVE OXIDATION SELECTIVE OXIDATION OF ALKYLBENZENES 7 6 1 2 SELECTIVE OXIDATION OF DIMETHYLIMIDAZOLE 7 6 2 CATION-RADICAL ROUTE TO GROUP DEPROTECTION 7 6 2 1 REMOVAL OF BUTOXYCARBONYL PROTECTIVE GROUP 7 6 2 2 REMOVAL OF METHOXYBENZYL PROTECTIVE GROUP 7 6 2 3 REMOVAL OF TRIMETHYLSILYL PROTECTIVE GROUP 7 6 3 SCISSION OF CARBON–CARBON BONDS 7 6 4 SYNTHON-IN? UENTIAL BOND SCISSION BOND FORMATION 7 8 OPPORTUNITIES ASSOCIATED WITH SRN1 REACTIONS 7 8 1 SUBSTRATE STRUCTURE 7 8 2 NATURE OF INTRODUCING GROUPS 7 8 3 REACTION MEDIUM 7 8 4 DARK SRN1 REACTIONS CONCLUSION ION-RADICAL ORGANIC CHEMISTRY IN ITS PRACTICAL APPLICABILITY 8 1 INTRODUCTION 8 2 ORGANIC ION-RADICALS IN MICROELECTRONICS 8 2 1 ION-RADICAL APPROACH TO MOLECULAR SWITCHES AND MODULATORS 8 2 3 LADDER POLYMERIZATION OF FLUORANTHENE-BASED CATION-RADICALS AS ROUTE TO ELECTROCHROMIC MATERIALS 8 3 ORGANIC METALS 8 4 SEMICONDUCTORS 8 5 ORGANIC MAGNETS 8 6 LUBRICATION IN TERMS OF ION-RADICAL ORGANIC CHEMISTRY 8 7 ION-RADICAL ORGANIC CHEMISTRY IN ITS CONTRIBUTIONS TO WOOD DELIGNI? CATION AND FOSSIL-FUEL DESULFURIZATION PAPER FABRICATION MANUFACTURE OF COMMERCIAL PRODUCTS FROM DELIGNI? CATION WASTES 8 7 3 DESULFURIZATION OF FOSSIL FUELS 8 8 CONCLUSION GENERAL OUTLOOK IMPORTANCE OF ION-RADICAL ORGANIC CHEMISTRY 9 2 SCIENTOMETRIC NOTES 9 3 PROSPECTS