Journal
NATURE CHEMISTRY
Volume 2, Issue 9, Pages 756-759Publisher
NATURE PUBLISHING GROUP
DOI: 10.1038/nchem.731
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Funding
- Ministry of Education, Culture, Sports, Science and Technology, Japan
- NRF/MEST [R31-2008-000-10010-0]
- Creative Research Initiatives Program
- [20108010]
- Grants-in-Aid for Scientific Research [20108001] Funding Source: KAKEN
- National Research Foundation of Korea [R31-2008-000-10010-0] Funding Source: Korea Institute of Science & Technology Information (KISTI), National Science & Technology Information Service (NTIS)
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Critical biological electron-transfer processes involving high-valent oxometal chemistry occur widely, for example in haem proteins [oxoiron(IV); Fe-IV(O)] and in photosystem II. Photosystem II involves Ca2+ as well as high-valent oxomanganese cluster species. However, there is no example of an interaction between metal ions and oxoiron(IV) complexes. Here, we report new findings concerning the binding of the redox-inactive metal ions Ca2+ and Sc3+ to a non-haem oxoiron(IV) complex, [(TMC)Fe-IV(O)](2+) (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane). As determined by X-ray diffraction analysis, an oxo-Sc3+ interaction leads to a structural distortion of the oxoiron(IV) moiety. More importantly, this interaction facilitates a two-electron reduction by ferrocene, whereas only a one-electron reduction process occurs without the metal ions. This control of redox behaviour provides valuable mechanistic insights into oxometal redox chemistry, and suggests a possible key role that an auxiliary Lewis acid metal ion could play in nature, as in photosystem II.
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