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Fine Control of the Redox Reactivity of a Nonheme Iron(III)–Peroxo Complex by Binding Redox‐Inactive Metal Ions
Author(s) -
Bae Seong Hee,
Lee YongMin,
Fukuzumi Shunichi,
Nam Wonwoo
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201610828
Subject(s) - chemistry , redox , reactivity (psychology) , nucleophile , metal , electrophile , metal ions in aqueous solution , electron transfer , electron paramagnetic resonance , reaction rate constant , medicinal chemistry , inorganic chemistry , photochemistry , catalysis , kinetics , organic chemistry , medicine , alternative medicine , pathology , physics , nuclear magnetic resonance , quantum mechanics
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)Fe III (O 2 )] + ‐M n + (M n + =Sc 3+ , Y 3+ , Lu 3+ , and La 3+ ), increases linearly with the increase of the Lewis acidity of the redox‐inactive metal ions (Δ E ), which is determined from the g zz values of EPR spectra of O 2 .− ‐M n + complexes. In contrast, the logarithm of the rate constants of the [(TMC)Fe III (O 2 )] + ‐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)Fe III (O 2 )] + ‐M n + complexes in electron‐transfer, electrophilic, and nucleophilic reactions.