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Updated: Jan 10, 2026

Stable Aqueous Suspensions of Manganese Ferrite Clusters with Tunable Nanoscale Dimension and Composition
Published on: February 5, 2022
Methyl-Containing Iron-Sulfur Cluster with FeMoco Geometry
Anna G Scott1,2, Serena DeBeer2, Theodor Agapie1
1Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States.
Abstract:
Biological production of NH3 from N2 in nitrogenases takes place at a complex octanuclear cluster displaying a bridging μ6-carbide ligand. The carbide is derived from a methyl group of a radical SAM enzyme. To gain insight into the reactivity and electronic structure impact of alkyl ligands, we have accessed iron sulfur clusters with terminal and bridging methyl groups. Treatment of the tetranuclear halide bridged cluster [Tp*MoFe3S3Cl4]2- with excess methyl Grignard results in the formation of a high spin octanuclear MoFeS cluster with bridging CH3 ligands. Spectroscopic characterization and computational analysis of this cluster, along with additional high spin MFeS (M = Mo or W) clusters with terminal alkyl ligands, suggest that MFeS clusters containing only Fe centers of oxidation states lower than Fe(III) achieve notably high spin states through ferromagnetic Fe-Fe interactions. Hydrogen and methane formation was demonstrated upon treatment with acid.
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