Tuning the Redox Properties of a Nonheme Iron(III)-Peroxo Complex Binding Redox-Inactive Zinc Ions by Water Molecules
Abstract
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.
- Authors:
-
- Ewha Womans Univ., Seoul (Korea)
- Osaka Univ., Suita (Japan); Japan Science and Technology Agency (JST), Suita (Japan). Advanced Low Carbon Technology Research and Development Program (ALCA)
- SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
- 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
- Publication Date:
- Research Org.:
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE; National Research Foundation of Korea (NRF); Japan Society for the Promotion of Science (JSPS)
- OSTI Identifier:
- 1261105
- Grant/Contract Number:
- AC02-76SF0051; NRF-2012R1A3A2048842; NRF-2010-00353; 2013R1A1A2062737
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry - A European Journal
- Additional Journal Information:
- Journal Volume: 21; Journal Issue: 30; Journal ID: ISSN 0947-6539
- Publisher:
- ChemPubSoc Europe
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; bioinorganic chemistry; metal–oxygen intermediates; oxygen-evolving complexes; redox reactions; water oxidation
Citation Formats
Lee, Yong-Min, Bang, Suhee, Yoon, Heejung, Bae, Seong Hee, Hong, Seungwoo, Cho, Kyung-Bin, Sarangi, Ritimukta, Fukuzumi, Shunichi, and Nam, Wonwoo. Tuning the Redox Properties of a Nonheme Iron(III)-Peroxo Complex Binding Redox-Inactive Zinc Ions by Water Molecules. United States: N. p., 2015.
Web. doi:10.1002/chem.201502143.
Lee, Yong-Min, Bang, Suhee, Yoon, Heejung, Bae, Seong Hee, Hong, Seungwoo, Cho, Kyung-Bin, Sarangi, Ritimukta, Fukuzumi, Shunichi, & Nam, Wonwoo. Tuning the Redox Properties of a Nonheme Iron(III)-Peroxo Complex Binding Redox-Inactive Zinc Ions by Water Molecules. United States. https://doi.org/10.1002/chem.201502143
Lee, Yong-Min, Bang, Suhee, Yoon, Heejung, Bae, Seong Hee, Hong, Seungwoo, Cho, Kyung-Bin, Sarangi, Ritimukta, Fukuzumi, Shunichi, and Nam, Wonwoo. Fri .
"Tuning the Redox Properties of a Nonheme Iron(III)-Peroxo Complex Binding Redox-Inactive Zinc Ions by Water Molecules". United States. https://doi.org/10.1002/chem.201502143. https://www.osti.gov/servlets/purl/1261105.
@article{osti_1261105,
title = {Tuning the Redox Properties of a Nonheme Iron(III)-Peroxo Complex Binding Redox-Inactive Zinc Ions by Water Molecules},
author = {Lee, Yong-Min and Bang, Suhee and Yoon, Heejung and Bae, Seong Hee and Hong, Seungwoo and Cho, Kyung-Bin and Sarangi, Ritimukta and Fukuzumi, Shunichi and Nam, Wonwoo},
abstractNote = {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.},
doi = {10.1002/chem.201502143},
journal = {Chemistry - A European Journal},
number = 30,
volume = 21,
place = {United States},
year = {Fri Jun 19 00:00:00 EDT 2015},
month = {Fri Jun 19 00:00:00 EDT 2015}
}
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