Synthesis of an All‐Ferric Cuboidal Iron–Sulfur Cluster [Fe III 4 S 4 (SAr) 4 ]

An unprecedented, super oxidized all-ferric iron-sulfur cubanoid cluster with all terminal thiolates, Fe4 S4 (STbt)4 (3) [Tbt=2,4,6-tris{bis(trimethylsilyl)methyl}phenyl], has been isolated from the reaction of the bis-thiolate complex Fe(STbt)2 (2) with elemental sulfur. This cluster 3 has been characterized by X-ray crystallography, zero-field 57 Fe Mossbauer spectroscopy, cyclic voltammetry, and other relevant physico-chemical methods. Based on all the data, the electronic ground state of the cluster has been assigned to be Stot =0.