120th General Meeting of the KCS

Type Poster Presentation
Area Inorganic Chemistry
Room No. Exhibition Hall 2+3
Time 10월 19일 (목요일) 11:00~12:30
Code INOR.P-28
Subject Tuning the Redox Reactivity of a Nonheme Iron(III)-Peroxo Species by Binding Redox-Inactive Metal Ions
Authors Seong Hee Bae, Yong-Min Lee1, Shunichi Fukuzumi2,*, Wonwoo Nam3,*
Department of Chemistry and Nano Science, Ewha Womans University, Korea
1Research Institute for Basic Sciences, Ewha Womans University, Korea
2Graduate School of Science and Engineering, Meijo University, Japan
3Department of Chemistry, Ewha Womans University, Korea
Abstract Redox-inactive metal ions are one of the most important co-factors involved in dioxygen activation and formation reactions by metalloenzymes. In this presentation, we have shown that the rate constants of electron transfer and C-H bond activation reactions by nonheme ion(III)-peroxo complexes binding redox- inactive metal ions, [(14-TMC)FeIII(O2)]+–Mn+ (Mn+ = Sc3+, Y3+, Lu3+, and La3+), increases proportionally with the increase of the Lewis acidity of the redox-inactive metal ions (ΔE). In contrast, the rate constants of the [(14-TMC)FeIII(O2)]+–Mn+ complexes in nucleophilic reactions with aldehydes decreases proportionally 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 [(14-TMC)FeIII(O2)]+–Mn+ complexes in electron-transfer, electrophilic, and nucleophilic reactions.
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