title: Fine Control of the Redox Reactivity of a Nonheme Iron(III)-Peroxo Complex by Binding Redox-Inactive Metal Ions.
abstract: Redox-inactive metal ions are one of the most important co-factors involved in dioxygen activation and formation reactions by metalloenzymes. In this study, we have shown that the logarithm of the rate constants of electron-transfer and C-H bond activation reactions by nonheme iron(III)-peroxo complexes binding redox-inactive metal ions, [(TMC)FeIII(O2)]+-Mn+(Mn+=Sc3+, Y3+, Lu3+, and La3+), increases linearly with the increase of the Lewis acidity of the redox-inactive metal ions (ΔE), which is determined from the gzzvalues of EPR spectra of O2.--Mn+complexes. In contrast, the logarithm of the rate constants of the [(TMC)FeIII(O2)]+-Mn+complexes in nucleophilic reactions with aldehydes decreases linearly as the ΔE value increases. Thus, the Lewis acidity of the redox-inactive metal ions bound to the mononuclear nonheme iron(III)-peroxo complex modulates the reactivity of the [(TMC)FeIII(O2)]+-Mn+complexes in electron-transfer, electrophilic, and nucleophilic reactions.
authors.affiliation: Department of Chemistry and Nano Science, Ewha Womans University, Seoul, 03760, Korea.
authors.forename: Seong Hee
authors.initials: SH
authors.lastname: Bae
authors.affiliation: Department of Chemistry and Nano Science, Ewha Womans University, Seoul, 03760, Korea.
authors.forename: Yong-Min
authors.initials: YM
authors.lastname: Lee
authors.affiliation: Department of Chemistry and Nano Science, Ewha Womans University, Seoul, 03760, Korea.|Faculty of Science and Engineering, SENTAN (Japan) Science and Technology Agency (JST), Meijo University, Nagoya, Aichi, 468-8502, Japan.
authors.forename: Shunichi
authors.initials: S
authors.lastname: Fukuzumi
authors.affiliation: Department of Chemistry and Nano Science, Ewha Womans University, Seoul, 03760, Korea.|State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical, Physics, Chinese Academy of Sciences, Lanzhou, 730000, China.
authors.forename: Wonwoo
authors.initials: W
authors.lastname: Nam
keywords: Lewis acidity; iron-peroxo intermediates; nonheme iron enzymes; reactive species; redox-inactive metal ions