TY - JOUR
T1 - Fine Control of the Redox Reactivity of a Nonheme Iron(III)–Peroxo Complex by Binding Redox-Inactive Metal Ions
AU - Bae, Seong Hee
AU - Lee, Yong Min
AU - Fukuzumi, Shunichi
AU - Nam, Wonwoo
N1 - Publisher Copyright:
© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2017/1/16
Y1 - 2017/1/16
N2 - 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.
AB - 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.
KW - Lewis acidity
KW - iron–peroxo intermediates
KW - nonheme iron enzymes
KW - reactive species
KW - redox-inactive metal ions
UR - http://www.scopus.com/inward/record.url?scp=85008970146&partnerID=8YFLogxK
U2 - 10.1002/anie.201610828
DO - 10.1002/anie.201610828
M3 - Article
C2 - 27943595
AN - SCOPUS:85008970146
SN - 1433-7851
VL - 56
SP - 801
EP - 805
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 3
ER -