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

✍ Scribed by Z. B. Alfassi; A. Harriman; S. Mosseri; P. Neta

Book ID
102446380
Publisher
John Wiley and Sons
Year
1986
Tongue
English
Weight
349 KB
Volume
18
Category
Article
ISSN
0538-8066

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✦ Synopsis

Trichloromethylperoxyl radicals were produced by pulse radiolysis of air saturated solutions containing CC1,. The rate constants for the reaction of CCI,O, radicals with zinc tetraphenylporphyrin (ZnTPP) were determined in various solvents. They were found to vary between 3 x lo7 and 3 x 1 0 ' M-' s-'. 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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