Abstract

The reaction of cobalt porphyrinate with organic peroxides in o-xylene has been studied using spectrophotometric titration, and its kinetic parameters have been determined. Imidazole has been shown to influence the process rate. A comparative analysis of the kinetic parameters of peroxide decomposition involving cobalt(III) porphyrinate and its zinc analogue has been carried out. A PM3 quantum-chemical method was used to optimize discrete molecules of the reagents and reaction intermediates, and their geometric parameters have been derived. Steric hindrances in the cobalt porphyrinate macrocycle and a considerable enhancement of distortion have been noticed to occur upon its reaction with a peroxide molecule.

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