Despite the postulated role of hydride species in the mechanism of N2 reduction by the iron-sulfur cluster at the active site of nitrogenase, there are no reports of any iron sulfide clusters with a hydride ligand.  The first iron sulfide hydride complex was synthesized by an unusual method, involving cleavage of a C-S bond by a metal hydride complex.  This reaction gives an anionic diiron(II) complex with bridging sulfide and hydride ligands, and releases an alkane.  Deuterium labeling studies have shown that the hydrogen of the newly formed C-H bond is derived from the hydride of the iron-hydride complex.  The novel species has been characterized by M�ssbauer, UV-vis, IR, and 1H NMR spectroscopy.  Electrochemical oxidation also formed a species tentatively assigned as an Fe(II)Fe(III) analogue.   The reactivity of the complexes with nitrogenase substrates will also be discussed. 

Synthesis and characterization of an iron sulfide hydride complex as a model for a nitrogenase intermediate

248th National Meeting (2014)

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