We found a match
Your institution may have rights to this item. Sign in to continue.
- Title
Fine Control of the Redox Reactivity of a Nonheme Iron(III)-Peroxo Complex by Binding Redox-Inactive Metal Ions.
- Authors
Bae, Seong Hee; Lee, Yong ‐ Min; Fukuzumi, Shunichi; Nam, Wonwoo
- 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)]+-M n+ (M n+=Sc3+, Y3+, Lu3+, and La3+), increases linearly with the increase of the Lewis acidity of the redox-inactive metal ions (Δ E), which is determined from the gzz values of EPR spectra of O2.−-M n+ complexes. In contrast, the logarithm of the rate constants of the [(TMC)FeIII(O2)]+-M n+ complexes in nucleophilic reactions with aldehydes decreases linearly as the Δ E 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)]+-M n+ complexes in electron-transfer, electrophilic, and nucleophilic reactions.
- Subjects
OXIDATION-reduction reaction; IRON compounds; METAL ions; METAL complexes; CARBON-hydrogen bonds; CHARGE exchange; NUCLEOPHILIC reactions
- Publication
Angewandte Chemie, 2017, Vol 129, Issue 3, p819
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.201610828