A high-valent iron-oxo corrolazine activates C-H bonds via hydrogen-atom transfer.

Oxidation of the Fe(III) complex (TBP(8)Cz)Fe(III) [TBP(8)Cz = octakis(4-tert-butylphenyl)corrolazinate] with O-atom transfer oxidants under a variety of conditions gives the reactive high-valent Fe(O) complex (TBP(8)Cz(+•))Fe(IV)(O) (2). The solution state structure of 2 was characterized by XAS [d(Fe-O) = 1.64 Å]. This complex is competent to oxidize a range of C-H substrates. Product analyses and kinetic data show that these reactions occur via rate-determining hydrogen-atom transfer (HAT), with a linear correlation for log k versus BDE(C-H), and the following activation parameters for xanthene (Xn) substrate: ΔH(++) = 12.7 ± 0.8 kcal mol(-1), ΔS(++) = -9 ± 3 cal K(-1) mol(-1), and KIE = 5.7. Rebound hydroxylation versus radical dimerization for Xn is favored by lowering the reaction temperature. These findings provide insights into the factors that control the intrinsic reactivity of Compound I heme analogues.