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

Z. B. Alfassi; A. Harriman; S. Mosseri; P. Neta

doi:10.1002/kin.550181203

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

Z. B. Alfassi, A. Harriman, S. Mosseri, P. Neta

Research output: Contribution to journal › Article › peer-review

20 Scopus citations

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.

Original language	English
Pages (from-to)	1315-1321
Number of pages	7
Journal	International Journal of Chemical Kinetics
Volume	18
Issue number	12
DOIs	https://doi.org/10.1002/kin.550181203
State	Published - 1 Jan 1986
Externally published	Yes

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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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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T1 - Rates and mechanisms of oxidation of ZnTPP by CCI3O2 radicals in various solvents

AU - Alfassi, Z. B.

AU - Harriman, A.

AU - Mosseri, S.

AU - Neta, P.

PY - 1986/1/1

Y1 - 1986/1/1

N2 - 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.

AB - 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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JO - International Journal of Chemical Kinetics

JF - International Journal of Chemical Kinetics

IS - 12

ER -

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

Abstract

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