Oxidation kinetics of Zn-5,15 bis(<Emphasis Type="Italic">ortho</Emphasis>-methoxyphenyl)-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, Ivanovo, Russia;(2) Ivanovo State University of Chemistry and Technology, ul. Akademicheskaya 1, Ivanovo, 153045, Russia |
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Abstract: | With the purpose of further investigation of the effect of the steric strain of the porphyrin macroring in metal porphyrins on their redox properties, kinetics of oxidation of Zn-5,15 bis(ortho-methoxyphenyl)-2,3,7,8,12,13.17,18-octamethylporphyrin with organic peroxides in o-xylene at 295°C were studied spectrophotometrically to show that this process leads to complete destruction of the complex. Kinetic characteristics (k ef, k v) of the process were evaluated. The structure of the zinc porphyrin and its oxidation intermediates were obtained by quantum-chemical calculations. Steris strains in the metal prophyrin macroring were revealed and shown to enhance in the course of the reaction. An effect of the degree of deformational strain on the oxidation rate was noted. |
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