Demonstration of the heterolytic O-O bond cleavage of putative nonheme iron(II)-OOH(R) complexes for Fenton and enzymatic reactions

Suhee Bang, Sora Park, Yong Min Lee, Seungwoo Hong, Kyung Bin Cho, Wonwoo Nam

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41 Scopus citations

Abstract

One-electron reduction of mononuclear nonheme iron(III) hydroperoxo (FeIII-OOH) and iron(III) alkylperoxo (FeIII-OOR) complexes by ferrocene (Fc) derivatives resulted in the formation of the corresponding iron(IV) oxo complexes. The conversion rates were dependent on the concentration and oxidation potentials of the electron donors, thus indicating that the reduction of the iron(III) (hydro/alkyl)peroxo complexes to their one-electron reduced iron(II) (hydro/alkyl)peroxo species is the rate-determining step, followed by the heterolytic O-O bond cleavage of the putative iron(II) (hydro/alkyl)peroxo species to give the iron(IV) oxo complexes. Product analysis supported the heterolytic O-O bond-cleavage mechanism. The present results provide the first example showing the one-electron reduction of iron(III) (hydro/alkyl)peroxo complexes and the heterolytic O-O bond cleavage of iron(II) (hydro/alkyl)peroxo species to form iron(IV) oxo intermediates which occur in nonheme iron enzymatic and Fenton reactions. Ironed out: One-electron reduction of mononuclear nonheme Fe III-OOH and FeIII-OOR complexes by ferrocene derivatives resulted in the formation of the corresponding FeIVO complexes. Reduction of the FeIII to FeII species is the rate-determining step (r.d.s.), followed by the heterolytic O-O bond cleavage to give the FeIVO complexes. The results provide the first example of this pathway to form FeIVO intermediates which occur in nonheme iron enzymatic and Fenton reactions.

Original languageEnglish
Pages (from-to)7843-7847
Number of pages5
JournalAngewandte Chemie - International Edition
Volume53
Issue number30
DOIs
StatePublished - 21 Jul 2014

Keywords

  • bioinorganic chemistry
  • enzyme models
  • iron
  • nonheme compounds
  • reaction mechanisms

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