Rates and mechanisms of oxidation of ZnTPP by CCI3O2 radicals in various solvents

Abstract
Trichloromethylperoxyl radicals were produced by pulse radiolysis of air saturated solutions containing CCl4. The rate constants for the reaction of CCl3O2 radicals with zinc tetraphenylporphyrin (ZnTPP) were determined in various solvents. They were found to vary between 3 × 107 and 3 × 109 M−1 s−1. The changes in rate constants result from complexation of ZnTPP with the different solvents, but did not correspond to changes in redox potential of ZnTPP. The rate constants were found to depend on the strength of the axial complexation, indicating an inner sphere mechanism whereby the radical binds to the metal prior to electron transfer.

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