Influence of imidazole on the kinetics of oxidation of 5,15-di(<Emphasis Type="Italic">ortho</Emphasis> -methyloxyphenyl)-2,3,7,8,12,13,17,18-octamethylporphyrin with organic peroxides in <Emphasis Type="Italic">o</Emphasis>-xylene |
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Authors: | O R Simonova S V Zaitseva O I Koifman |
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Institution: | (1) Institute of Solution Chemistry, Russian Academy of Sciences, ul. Akademicheskaya 1, Ivanovo, 153045, Russia;(2) Ivanovo State University of Chemical Technology, Ivanovo, Russia |
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Abstract: | The structure of zinc 5,15-di(ortho -methyloxyphenyl)-2,3,7,8,12,13,17,18-octamethylporphyrin was studied by spectrophotometry and computer simulation. Its properties in the reaction with organic peroxides in o-xylene in the presence of imidazole were studied at 295 K. The apparent and true rate constants for this process were calculated. The metalloporphyrin chromophore was found to decompose completely during the interaction of the zinc porphyrin (ZnP) with peroxides. The influence of imidazole on the reaction rate was revealed. The geometric characteristics of the optimized ZnP structure and intermediates of the oxidation were obtained by the PM3 quantum-chemical method. The deformational strains in the ZnP macrocycle were found to increase during the reaction. |
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