Kinetic and mechanistic studies of the reactions of selected aliphatic radicals with metal complexes and the decomposition of organoperoxy cobalt complexes

Abstract

The reaction of vanadixjm(II) with the 2-hydroxy-2propyl radical 23 Organic products 23 Inorganic product 25 The reaction of vanadium(II) with the 1-ethoxyethyl radical The reactions of (H2O)2Co^^([14]aneN^) with radicals 29 Organocobalt(III) intermediate 30 Kinetics 31 The reactions of vanadium(II) with radicals Primary deuterium isotope effect The reactions of (H2O) 2^0^^ ([ 14] aneN^) with radicals INTERPRETATION AND DISCUSSION Mechanisms of the Oxidation of Vanadium(II) Ion with Free Radicals Competitive kinetics The roles of radicals and vanadium(II) ion Reaction mechanisms Outer-sphere electron transfer 46 Hydrogen atom abstraction 47 V-C bond formation followed by acidolysis 48 Preequilibrium process 49 II 2+ Mechanisms of Reactions of Co ([14]aneN^) with Radicals 50 Inner-sphere mechanism 51 The pathway of the Co-C bond formation 51 The decomposition of the Co-C bond 52 Reactions of hydridocobalt complex 54 Outer-sphere electron transfer 54 CONCLUSIONS 57a iv PART II. REACTIONS OF (ALKYLPEROXY)COBALOXIMES IN ACIDIC AQUEOUS SOLUTIONS 58 Organic compounds 70 Cyclopentyl hydroperoxide 70 Miscellaneous reagents 71 Methods 71 Characterization of the synthesized compounds 71 Product identification 75 Kinetics 87 Spectrophotometry 87 Gas chromatography 91 RESULTS 93 Product Analysis 93 NMR analysis 93 lodometric titration 100 Kinetics 101