Add time:07/14/2019 Source:sciencedirect.com
The reactivity of the previously reported pentadentate low-spin (S = 1) oxoiron(IV) complex, [FeIV(O)(asN4Py)] (2) (asN4Py = N,N-bis(2-pyridylmethyl)-1,2-di(2-pyridyl)ethylamine), has been investigated in the oxidation reaction of 2,6-di-tert-butylphenol derivatives. Detailed kinetic, and mechanistic studies (kinetic isotope effect (KIE) of 4.52, and Hammett correlation with ρ = −1.83), lead to the conclusion that the rate-determining step in this reaction involves direct hydrogen-atom transfer (HAT) from the phenol by the oxoiron(IV) species, in contrast to the heme-type horseradish peroxidase (HRP) system.
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