Heating the electron-deficient [Os₃(CO)₈(μ-H)(μ₃-Ph₂PCH₂P(Ph)C₆H₄)] (1) and Ph₃GeSPh in benzene at 80 °C led to the thiolato bridged compounds, [Os₃(CO)₈(μ-H)(μ-SPh)(μ-dppm)] (2) and [Os₃(CO)₇(μ-H)(μ-SPh)(μ₃-SC₆H₄)(μ-dppm)] (3), formed by cleavage of Ge–S and C–S bonds of the ligand, in 40% and 17% yields, respectively. Both compounds 2 and 3 have been characterized by a combination of elemental analysis, infrared and ¹H NMR spectroscopic data together with single crystal X-ray crystallography. Compound 3 contains an open triangle of osmium atoms bridged by a SPh and SC₆H₄ ligands on opposite sides of the cluster with a dppm ligand bridging one of the Os–Os edges. Compound 2 consists of a closed triangular cluster of osmium atoms with a bridging SPh, and a bridging hydride ligand on the same Os–Os edge, and a dppm ligand bridging one of the remaining Os–Os edges.