Fine Control of the Redox Reactivity of a Nonheme Iron(III)–Peroxo Complex by Binding Redox-Inactive Metal Ions

Seong Hee Bae, Yong Min Lee, Shunichi Fukuzumi, Wonwoo Nam

Research output: Contribution to journalArticlepeer-review

35 Scopus citations

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)]+-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.

Original languageEnglish
Pages (from-to)801-805
Number of pages5
JournalAngewandte Chemie - International Edition
Volume56
Issue number3
DOIs
StatePublished - 16 Jan 2017

Keywords

  • iron–peroxo intermediates
  • Lewis acidity
  • nonheme iron enzymes
  • reactive species
  • redox-inactive metal ions

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