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Tuning the Redox Properties of a Nonheme Iron(III)-Peroxo Complex Binding Redox-Inactive Zinc Ions by Water Molecules
- Title
- Tuning the Redox Properties of a Nonheme Iron(III)-Peroxo Complex Binding Redox-Inactive Zinc Ions by Water Molecules
- Authors
- Lee, Yong-Min; Bang, Suhee; Yoon, Heejung; Bae, Seong Hee; Hong, Seungwoo; Cho, Kyung-Bin; Sarangi, Ritimukta; Fukuzumi, Shunichi; Nam, Wonwoo
- Ewha Authors
- 남원우; Shunichi Fukuzumi; 이용민
- SCOPUS Author ID
- 남원우; Shunichi Fukuzumi; 이용민
- Issue Date
- 2015
- Journal Title
- CHEMISTRY-A EUROPEAN JOURNAL
- ISSN
- 0947-6539
1521-3765
- Citation
- CHEMISTRY-A EUROPEAN JOURNAL vol. 21, no. 30, pp. 10676 - 10680
- Keywords
- bioinorganic chemistry; metal-oxygen intermediates; oxygen-evolving complexes; redox reactions; water oxidation
- Publisher
- WILEY-V C H VERLAG GMBH
- Indexed
- SCI; SCIE; SCOPUS
- Document Type
- Article
- Abstract
- Redox-inactive metal ions play important roles in tuning chemical properties of metal-oxygen intermediates. Herein we report the effect of water molecules on the redox properties of a nonheme iron(III)-peroxo complex binding redox-inactive metal ions. The coordination of two water molecules to a Zn2+ ion in (TMC)Fe-III-(O-2)-Zn(CF3SO3)(2) (1-Zn2+) decreases the Lewis acidity of the Zn2+ ion, resulting in the decrease of the one-electron oxidation and reduction potentials of 1-Zn2+. This further changes the reactivities of 1-Zn2+ in oxidation and reduction reactions; no reaction occurred upon addition of an oxidant (e.g., cerium(IV) ammonium nitrate (CAN)) to 1-Zn2+, whereas 1-Zn2+ coordinating two water molecules, (TMC)Fe-III-(O-2)-Zn(CF3SO3)(2)-(OH2)(2) [1-Zn2+-(OH2)(2)], releases the O-2 unit in the oxidation reaction. In the reduction reactions, 1-Zn2+ was converted to its corresponding iron(IV)-oxo species upon addition of a reductant (e.g., a ferrocene derivative), whereas such a reaction occurred at a much slower rate in the case of 1-Zn2+-(OH2)(2). The present results provide the first biomimetic example showing that water molecules at the active sites of metalloenzymes may participate in tuning the redox properties of metal-oxygen intermediates.
- DOI
- 10.1002/chem.201502143
- Appears in Collections:
- 자연과학대학 > 화학·나노과학전공 > Journal papers
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