Chalcogenide-capped triruthenium clusters: X-ray structures of [Ru3(CO)6(μ3-CO){P(C4H3S)3}(μ-dppm)(μ3-O)] and [(μ-H)2Ru3(CO)6{P(C4H3S)3}(μ-dppm)(μ3-S)]

Treatment of [Ru3(CO)9{P(C4H3S)3}(μ-dppm)] (1) [dppm = bis(diphenylphosphino)methane] with molecular oxygen in benzene at 60 °C affords oxo-capped [Ru3(CO)6(μ3-CO){P(C4H3S)3}(μ-dppm)(μ3-O)] (2), while with elemental sulfur and selenium related chalcogenide-capped clusters [Ru3(CO)6(μ3-CO){P(C4H3S)3}(μ-dppm)(μ3-E)] (3, E = S; 5, E = Se) and bis(chalcogenide) clusters [Ru3(CO)6{P(C4H3S)3}(μ-dppm)(μ3-E)2] (4, E = S; 6, E = Se) result. Reaction of 1 with H2S in refluxing THF affords the previously reported [(μ-H)2Ru3(CO)7(μ-dppm)(μ3-S)] (7) together with the new sulfido-capped dihydride [(μ-H)2Ru3(CO)6{P(C4H3S)3}(μ-dppm)(μ3-S)] (8). All new compounds have been characterized by spectroscopic data, and 2 and 8 by single-crystal X-ray diffraction analyses. Oxo-capped 2 consists of a triangular ruthenium framework capped on opposite sides by oxo and carbonyl groups, while 8 consists of a ruthenium triangle by a capping sulfido ligand and two inequivalent bridging hydride ligands.