Id. Cunningham et al., Kinetics and mechanism of the hydrogen peroxide oxidation of a pentafluorophenyl-substituted iron(III) porphyrin, J CHEM S P2, (10), 1999, pp. 2133-2139
Citations number
50
Categorie Soggetti
Physical Chemistry/Chemical Physics
Journal title
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2
Kinetic analysis of the (F20TPP)FeCl-catalysed H2O2 oxidation of 3-hydroxy-
2-(trans-4-tert-butylcyclohexyl)methylnaphtho-1,4-quinone is consistent wit
h rapid reaction of the organic substrate with an oxoperferryl intermediate
[(F20TPP.+)Fe-IV=O] formed in the first and rate-limiting step. A second-o
rder rate constant for oxidation of the catalyst of 22 +/- 5 dm(3) mol(-1)
s(-1) is found, a value lower than previously reported. In the absence of t
he organic substrate, H2O2 oxidises the catalyst to an oxoferryl species (F
20TPP)Fe-IV=O, probably via the oxoperferryl species. This oxoferryl compou
nd is itself bleached by H2O2 with a second-order rate constant of 0.081 +/
- 0.004 dm(3) mol(-1) s(-1) probably involving oxidation of the porphyrin r
ing.