A general method for metallocluster site-differentiation

The deployment of metalloclusters in applications such as catalysis and materials synthesis requires robust methods for site-differentiation: the conversion of clusters with symmetric ligand spheres to those with unsymmetrical ligand spheres. However, imparting precise patterns of site-differentiation is challenging because, compared with mononuclear complexes, the ligands bound to clusters exert limited spatial and electronic influence on one another. Here, we report a method that employs sterically encumbering ligands to bind to only a subset of a cluster's coordination sites. Specifically, we show that homoleptic, phosphine-ligated Fe-S clusters undergo ligand substitution with N-heterocyclic carbenes (NHCs) to give heteroleptic clusters in which the resultant clusters' site-differentiation patterns are encoded by the steric profile of the incoming NHC. This method affords access to every site-differentiation pattern for cuboidal [Fe₄S₄] clusters and can be extended to other cluster types, particularly in the stereoselective synthesis of site-differentiated Chevrel-type [Fe₆S₈] clusters.