Nitrogenase performs the difficult multielectron reduction of N<sub>2</sub> to NH<sub>3</sub> at the iron-molybdenum cofactor (FeMoco), which is a cluster of high-spin iron ions bridged by sulfide and carbide. There is no precedent for this combination of structural features in any iron cluster, hindering chemists' ability to evaluate the feasibility of potential mechanisms of substrate reduction at the FeMoco. The presence of Fe-C bonds in an iron-sulfur cluster is especially intriguing, and leads to questions about the nature of Fe-C bonding between high-spin iron and bridging C groups. This presentation will describe the preparation and study of compounds with sulfur and carbon bridges between high-spin iron sites. Study of the structures and reactivity characteristics of these isolable clusters helps to answer structural, spectroscopic, and mechanistic questions using well-characterized synthetic compounds.

Carbon- and sulfur-bridged iron clusters of relevance to nitrogenase

255th National Meeting (2018)

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