One- to two-electron reduction of an [FeFe]-hydrogenase active site mimic: The critical role of fluxionality of the [2Fe2S] core

Greg A.N. Felton, Benjamin J. Petro, Richard S. Glass, Dennis L. Lichtenberger, Dennis H. Evans

Research output: Contribution to journalArticle

66 Scopus citations


(Figure Presented) The one- to two-electron reduction of μ-(1,2-ethanedithiolato)diironhexacarbonyl that has been observed under electrochemical conditions is dependent on scan rate and temperature, suggesting activation of a structural rearrangement. This structural rearrangement is attributed to fluxionality of the [2Fe2S] core in the initially formed anion. Computations support this assessment. Upon an initial one-electron reduction, the inherent fluxionality of the [2Fe2S] complex anion allows for a second one-electron reduction at a less negative potential to form a dianionic species. The structure of this dianion is characterized by a rotated iron center, a bridging carbonyl ligand, and, most significantly, a dissociated Fe-S bond. This fluxionality of the [2Fe2S] core upon reduction has direct implications for the chemistry of [FeFe]-hydrogenase mimics and for iron-sulfur cluster chemistry in general.

Original languageEnglish (US)
Pages (from-to)11290-11291
Number of pages2
JournalJournal of the American Chemical Society
Issue number32
StatePublished - Aug 19 2009


ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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