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 [Ru-3(CO)(9){P(C4H3S)(3)}(mu-dppm)] (1) [dppm = bis(diphenylphosphino)methane] with molecular oxygen in benzene at 60 degrees C affords oxo-capped [Ru-3(CO)(6)(mu(3)-CO){P(C4H3S)(3)}(mu-dppm)-(mu(3)-O)] (2), while with elemental sulfur and selenium related chalcogenide-capped clusters [Ru-3(CO)(6)(mu(3)-CO){P(C4H3S)(3)}(mu-dppm)(mu(3)-E)] (3, E= S; 5, E = Se) and bis(chalcogenide) clusters [Ru-3(CO)(6){P(C4H3S)(3)}(mu-dppm)(mu(3)-E)(2)] (4, E= S; 6, E = Se) result. Reaction of 1 with H2S in refluxing THF affords the previously reported [(mu-H)(2)Ru-3(CO)(7)(mu-dppm)(mu(3)-S)] (7) together with the new sulfido-capped dihydride [(mu-H)(2)Ru-3(CO)(6){P(C4H3S)(3)}(mu-dppm)(mu(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. (C) 2011 Elsevier B. V. All rights reserved.