Crystal structure of a metal ion-bound oxoiron(IV) complex and implications for biological electron transfer

Shunichi Fukuzumi, Yuma Morimoto, Hiroaki Kotani, Pance Naumov, Yong Min Lee, Wonwoo Nam

    Research output: Contribution to journalArticle

    Abstract

    Critical biological electron-transfer processes involving high-valent oxometal chemistry occur widely, for example in haem proteins [oxoiron(IV); FeIV (O)] and in photosystem II. Photosystem II involves Ca 2+ 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)FeIV (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.

    Original languageEnglish (US)
    Pages (from-to)756-759
    Number of pages4
    JournalNature Chemistry
    Volume2
    Issue number9
    DOIs
    StatePublished - Sep 1 2010

    Fingerprint

    Photosystem II Protein Complex
    Metal ions
    Crystal structure
    Electrons
    Lewis Acids
    Heme
    X ray diffraction analysis
    Proteins
    Acids
    Oxidation-Reduction

    ASJC Scopus subject areas

    • Chemistry(all)
    • Chemical Engineering(all)

    Cite this

    Crystal structure of a metal ion-bound oxoiron(IV) complex and implications for biological electron transfer. / Fukuzumi, Shunichi; Morimoto, Yuma; Kotani, Hiroaki; Naumov, Pance; Lee, Yong Min; Nam, Wonwoo.

    In: Nature Chemistry, Vol. 2, No. 9, 01.09.2010, p. 756-759.

    Research output: Contribution to journalArticle

    Fukuzumi, S, Morimoto, Y, Kotani, H, Naumov, P, Lee, YM & Nam, W 2010, 'Crystal structure of a metal ion-bound oxoiron(IV) complex and implications for biological electron transfer', Nature Chemistry, vol. 2, no. 9, pp. 756-759. https://doi.org/10.1038/nchem.731
    Fukuzumi, Shunichi ; Morimoto, Yuma ; Kotani, Hiroaki ; Naumov, Pance ; Lee, Yong Min ; Nam, Wonwoo. / Crystal structure of a metal ion-bound oxoiron(IV) complex and implications for biological electron transfer. In: Nature Chemistry. 2010 ; Vol. 2, No. 9. pp. 756-759.
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