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Oxidized and reduced [2Fe–2S] clusters from an iron(I) synthon

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Abstract

Synthetic [2Fe–2S] clusters are often used to elucidate ligand effects on the reduction potentials and spectroscopy of natural electron-transfer sites, which can have anionic Cys ligands or neutral His ligands. Current synthetic routes to [2Fe–2S] clusters are limited in their feasibility with a range of supporting ligands. Here, we report a new synthetic route to synthetic [2Fe–2S] clusters, through oxidation of an iron(I) source with elemental sulfur. This method yields a neutral diketiminate-supported [2Fe–2S] cluster in the diiron(III)-oxidized form. The oxidized [2Fe–2S] cluster can be reduced to a mixed valent iron(II)–iron(III) compound. Both the diferric and reduced mixed valent clusters are characterized using X-ray crystallography, Mössbauer spectroscopy, EPR spectroscopy and cyclic voltammetry. The reduced compound is particularly interesting because its X-ray crystal structure shows a difference in Fe–S bond lengths to one of the iron atoms, consistent with valence localization. The valence localization is also evident from Mössbauer spectroscopy.

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Acknowledgments

Funding was provided by the National Institutes of Health (GM065313). We thank Eckhard Bill and Wilda Vargas for preliminary experiments, and Richard Lewis for checking reproducibility of the syntheses.

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Authors and Affiliations

  1. Department of Chemistry, Yale University, 225 Prospect Street, New Haven, CT, 06520, USA

    Megan E. Reesbeck, Brandon Q. Mercado, David Vinyard & Patrick L. Holland

  2. Department of Chemistry, University of Rochester, 120 Trustee Road, Rochester, NY, 14627, USA

    Meghan M. Rodriguez & William W. Brennessel

Authors
  1. Megan E. Reesbeck
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  2. Meghan M. Rodriguez
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  3. William W. Brennessel
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  4. Brandon Q. Mercado
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  6. Patrick L. Holland
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Corresponding author

Correspondence to Patrick L. Holland.

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Reesbeck, M.E., Rodriguez, M.M., Brennessel, W.W. et al. Oxidized and reduced [2Fe–2S] clusters from an iron(I) synthon. J Biol Inorg Chem 20, 875–883 (2015). https://doi.org/10.1007/s00775-015-1272-4

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  • DOI: https://doi.org/10.1007/s00775-015-1272-4

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