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

J Am Chem Soc. 2023 Jan 11;145(1):2-6. doi: 10.1021/jacs.2c04826. Epub 2022 Dec 20.

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.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, N.I.H., Extramural
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Iron* / chemistry
  • Iron-Sulfur Proteins* / chemistry
  • Ligands
  • Oxidation-Reduction
  • Sulfur / chemistry

Substances

  • Iron
  • barban
  • Ligands
  • Iron-Sulfur Proteins
  • Sulfur