Fine Control of the Redox Reactivity of a Nonheme Iron(III)–Peroxo Complex by Binding Redox-Inactive Metal Ions
- 주제(키워드) iron–peroxo intermediates , Lewis acidity , nonheme iron enzymes , reactive species , redox-inactive metal ions
- 등재 SCIE, SCOPUS
- 발행기관 Wiley-VCH Verlag
- 발행년도 2017
- 총서유형 Journal
- URI http://www.dcollection.net/handler/ewha/000000141617
- 본문언어 영어
- Published As http://dx.doi.org/10.1002/anie.201610828
- 저작권 이화여자대학교 논문은 저작권에 의해 보호받습니다.
초록/요약
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 gzz values 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. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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