Chalcogenide-capped triruthenium clusters: X-ray structures of [Ru _3(CO)_6(μ_3-CO){P(C_4H _3S)_3}(μ-dppm)(μ_3-O)] and [(μ-H) _2Ru_3(CO)_6{P(C_4H_3S) _3}(μ-dppm)(μ_3-S)]

摘要

Treatment of [Ru_3(CO)_9{P(C_4H _3S)_3}(μ-dppm)] (1) [dppm = bis(diphenylphosphino) methane] with molecular oxygen in benzene at 60 °C affords oxo-capped [Ru_3(CO)_6(μ_3-CO){P(C_4H _3S)_3}(μ-dppm)(μ_3-O)] (2), while with elemental sulfur and selenium related chalcogenide-capped clusters [Ru 3(CO)6(μ3-CO){P(C4H 3S)3}(μ-dppm)(μ3-E)] (3, E = S; 5, E = Se) and bis(chalcogenide) clusters [Ru_3(CO)_6{P(C _4H_3S)_3}(μ-dppm)(μ_3-E) _2] (4, E = S; 6, E = Se) result. Reaction of 1 with H_2S in refluxing THF affords the previously reported [(μ-H)_2Ru _3(CO)_7(μ-dppm)(μ_3-S)] (7) together with the new sulfido-capped dihydride [(μ-H)_2Ru_3(CO) _6{P(C_4H_3S)_3}(μ-dppm) (μ_3-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.