Facile reduction of 2,2′-dithiobisbenzothiazole by the mediation of metal-to-ligand charge transfer or by internal reducing equivalent is demonstrated. It leads to various binding modes of thiolates (κ¹, κ², μ) in a series of mononuclear and dinuclear ruthenium complexes. The dinuclear complex exhibited electron transfer processes similar to a [2Fe-2S] cluster.