Abstract
The presence of a carbide ligand in the active site of nitrogenases remains an unusual example of organometallic chemistry employed by a protein. Carbide incorporation into the MFe(7)S(9)C cluster involves complex biosynthesis, but analogous synthetic methodologies are limited. Herein, we present a new synthetic strategy for incorporating carbon based bridging ligands into iron-sulfur clusters. Starting from a halide precursor, a WFe(3)S(3) cluster displaying three terminal alkyl ligands and an open Fe(3) face was prepared. Oxidation results in loss of alkane and formation of a μ(3)-carbyne. Characterization of these clusters and mechanistic studies are presented.