Kinetics and mechanisms of the reactions of aliphatic free radicals with organocobaloximes and fluoropentaamminecobalt(III) ion, and of iron(III) with methylrhodoxime

Abstract

Cobaloxlmes Organochromlurn reagents 19 Miscellaneous reagents Methods Analyses and characterizations 23 % Co analysis Product analyses Rate determinations DESIGN OF COMPETITION EXPERIMENTS •CH(CH^)0C2H^ Radical-CfCHgigOH Radical RESULTS 41 Reactions of the-CHfCHgïOCgHg Radical with Organocobaloximes 41 Benzyl(aquo)cobaloxime, PhCHgCofdmgHjgOHg 4l Other alkylcobaloxlmes, RCo(dmgH)_OH_ (R = CH,, CH"CH_, and Reactions of the "CfCH^jgOH Radical with Organocobaloximes 55 Benzyl(aquo)cobaloxime, PhCHgCofdmgHjgOHg 55 Other alkylcobaloxlmes, RCo(dmgH)_0H_ (R = CH,, CH«CH_, and 63 î i I Products of the Coupling Reactions Between Selected Free Radicals and Benzy1(aquo)cobaloxime 72 Preparation of a Large Sample of 2-Methyl-1-phenyl-2-propano1 79 Protonation Constant for Benzyl coba loxi me 80 DISCUSSION 84 Mechanistic Alternatives 86 Electron transfer mechanisms 88 Bimolecular homolytic substitution 89 Addition-elimination mechanisms 91 Fate of the 0-radicals from 2-propanol and ethanol 97 Conclusions 99 PART II. REDUCTION OF FLUORGPENTAAMMINECOBALT(III), CoCNHgigF^*, BY 2-HYDR0XY-2-PR0PYL AND a-ETHOXYETHYL RADICALS 100