Kinetics of the Reactions of 'Capped' Zinc 5,15-(1,4-Bis(2'- phenylenoxymethylene)-phenyl)-2,8,12,18-tetramethyl-3,7,13,17- tetrabutylporphyrinate) with Organic Peroxides in o-Xylene

摘要

The reactions of "capped" zinc porphyrinate with organic peroxides were studied by spectrophotometry. The reaction rate constant was determined (0.417 s~(-1) mol~(-1) l~(-1)). The variation of the imidazole concentration in the reaction mixture changed the composition of the reactants and increased the reaction rate by 1.3-5.3 times. The geometric characteristics of isolated molecules of the reactants and intermediates were obtained by the PM3 quantum-chemical method. The calculated structures of these compounds were flat and characterized by a distorted macrocycle. An increase in steric strains of the macrocycles of the molecular complex with imidazole and of the imidazole-containing reaction intermediates was shown.