Demonstration of the heterolytic O-O bond cleavage of putative nonheme iron(II)-OOH(R) complexes for fenton and enzymatic reactions
- 등재 SCIE, SCOPUS
- 발행기관 John Wiley & Sons Ltd.
- 발행년도 2014
- 총서유형 Journal
- URI http://www.dcollection.net/handler/ewha/000000097810
- 본문언어 영어
- Published As http://dx.doi.org/10.1002/anie.201404556
- 저작권 이화여자대학교 논문은 저작권에 의해 보호받습니다.
초록/요약
One-electron reduction of mononuclear nonhemeiron(III) hydroperoxo (FeIIIOOH) and iron(III) alkylperoxo(FeIIIOOR) complexes by ferrocene (Fc) derivatives resultedin the formation of the corresponding iron(IV) oxo complexes.The conversion rates were dependent on the concentration andoxidation potentials of the electron donors, thus indicating thatthe reduction of the iron(III) (hydro/alkyl)peroxo complexesto their one-electron reduced iron(II) (hydro/alkyl)peroxospecies is the rate-determining step, followed by the heterolyticOO bond cleavage of the putative iron(II) (hydro/alkyl)per-oxo species to give the iron(IV) oxo complexes. Productanalysis supported the heterolytic OO bond-cleavage mech-anism. The present results provide the first example showingthe one-electron reduction of iron(III) (hydro/alkyl)peroxocomplexes and the heterolytic OO bond cleavage of iron(II)(hydro/alkyl)peroxo species to form iron(IV) oxo intermedi-ates which occur in nonheme iron enzymatic and Fentonreactions
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