Synthesis of a Fe₃–Carbyne Motif by Oxidation of an Alkyl Ligated Iron–Sulfur (WFe₃S₃) Cluster

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 MFe7S9C 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 WFe3S3 cluster displaying three terminal alkyl ligands and an open Fe3 face was prepared. Oxidation results in loss of alkane and formation of a μ3-carbyne. Characterization of these clusters and mechanistic studies are presented.

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