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.
- Hydrogen-atom abstraction
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry
- Materials Chemistry