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Title: Tuning the Redox Properties of a Nonheme Iron(III)-Peroxo Complex Binding Redox-Inactive Zinc Ions by Water Molecules

Journal Article · · Chemistry - A European Journal
 [1];  [1];  [2];  [1];  [1];  [1];  [3];  [4];  [1]
  1. Ewha Womans Univ., Seoul (Korea)
  2. Osaka Univ., Suita (Japan); Japan Science and Technology Agency (JST), Suita (Japan). Advanced Low Carbon Technology Research and Development Program (ALCA)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
  4. Osaka Univ., Suita (Japan); Japan Science and Technology Agency (JST), Suita (Japan). Advanced Low Carbon Technology Research and Development Program (ALCA); Meijo Univ., Nagoya (Japan); Japan Science and Technology Agency (JST), Nagoya (Japan) Advanced Low Carbon Technology Research and Development Program (ALCA) and SENTAN
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Here we report redox-inactive metal ions play important roles in tuning chemical properties of metal–oxygen intermediates. We describe 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)FeIII-(O2)-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)FeIII-(O2)-Zn(CF3SO3)2-(OH2)2 [1-Zn2+-(OH2)2], releases the O2 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. Finally, 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.

Research Organization:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Organization:
USDOE; National Research Foundation of Korea (NRF); Japan Society for the Promotion of Science (JSPS)
Grant/Contract Number:
AC02-76SF0051; NRF-2012R1A3A2048842; NRF-2010-00353; 2013R1A1A2062737
OSTI ID:
1261105
Journal Information:
Chemistry - A European Journal, Vol. 21, Issue 30; ISSN 0947-6539
Publisher:
ChemPubSoc EuropeCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 12 works
Citation information provided by
Web of Science

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
bioinorganic chemistry
metal–oxygen intermediates
oxygen-evolving complexes
redox reactions
water oxidation