S42− Rings, Disulfides, and Sulfides in Transition‐Metal Complexes: The Subtle Interplay of Oxidation and Structure

Coming together, breaking apart: A theoretical analysis of the oxidative coupling of two metal-coordinated disulfide species to a S42− rectangle provides an opening to a reexamination of a number of compounds hitherto considered to be disulfide complexes. An electronic framework helps explain how the nature of the metal controls inner redox processes and the alternative stabilization of S42− or 2 S22− (or S2−) species (see scheme).