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Small, coordinatively unsaturated iron-sulfur clusters are conceived as building blocks for the diverse set of shapes of iron-sulfur clusters in biological and synthetic chemistry. Here we describe a synthetic method for preparing [2Fe-1S] clusters containing two iron(II) ions, which are supported by a relatively unhindered β-diketiminate supporting ligand. The [2Fe-1S] cluster can be isolated in the presence of trimethylphosphine, and the compound with one PMe 3 on each iron(II) ion has been crystallographically characterized. The PMe 3 ligands may be removed with B(C 6 F 5 ) 3 to give a spectroscopically characterized species with solvent ligands. This species is a versatile synthon for [2Fe-2S], [4Fe-3S], and [10Fe-8S] clusters. Crystallographic characterization of the 10Fe cluster shows that it has all iron(II) ions, and the core has two [4Fe-4S] cubes that share a face in a novel arrangement. This cluster also has two iron sites that are coordinated to solvent donors, suggesting the potential for using this type of cluster for reactivity in the future.

A [2Fe–1S] Complex That Affords Access to Bimetallic and Higher-Nuclearity Iron–Sulfur Clusters