Electron-Transfer and Redox Reactivity of High-Valent Iron Imido and Oxo Complexes with the Formal Oxidation States of Five and Six

We report for the first time electron-transfer (ET) properties of mononuclear nonheme iron-oxo and-imido complexes with the formal oxidation states of five and six, such as an iron(V)-imido TAML cation radical complex, which is formally an iron(VI)-imido complex [Fe^V(NTs)(TAML^+â¢)] (1; NTs = tosylimido), an iron(V)-imido complex [Fe^V(NTs)(TAML)]^- (2), and an iron(V)-oxo complex [Fe^V(O)(TAML)]^- (3). The one-electron reduction potential (E_red vs SCE) of 1 was determined to be 0.86 V, which is much more positive than that of 2 (0.30 V), but the E_red of 3 is the most positive (1.04 V). The rate constants of ET of 1-3 were analyzed in light of the Marcus theory of adiabatic outer-sphere ET to determine the reorganization energies (λ) of ET reactions with 1-3; the λ of 1 (1.00 eV) is significantly smaller than those of 2 (1.98 eV) and 3 (2.25 eV) because of the ligand-centered ET reduction of 1 as compared to the metal-centered ET reduction of 2 and 3. In oxidation reactions, reactivities of 1-3 toward the nitrene transfer (NT) and oxygen atom transfer (OAT) to thioanisole and its derivatives and the C-H bond activation reactions, such as the hydrogen atom transfer (HAT) of 1,4-cyclohexadiene, were compared experimentally. The differences in the redox reactivity of 1-3 depending on the reaction types, such as NT and OAT versus HAT, were interpreted by performing density functional theory calculations, showing that the ligand-centered reduction seen on ET reactions can switch to metal-centered reduction in NT and HAT.