STRUCTURAL CHARACTERIZATION OF THE HEXANUCLEAR CLUSTER [Os_6(CO)_(12)(μ_3-S)_4(μ-dppm)_2]AND THE TRINUCLEAR CLUSTER [Os_3(CO)_6(μ_3-S)_2(μ-dppm)(PPh_3)]

摘要

The solid-state structures of the hexanuclear compound [Os_6(CO)_(12)(μ_3-S)_4(μ-dppm)_2] (3), synthesized from the Me_3NO initiated self condensation of [Os_3(CO)_7(μ_3-S)_2(μ-dppm)] (1), and the trinuclear compound [Os_3(CO)_6(μ_3-S)_2(μ-dppm)(PPh_3)] (4), synthesized from the reaction of [Os_3(CO)_6(μ_3-S)_2(Me_3N)(μ-dppm)] (2) with PPh_3, have been determined by single crystal X-ray diffraction methods. Compound 3 crystallizes in the monoclinic space group P2_1 with a = 13.8978(2), b = 39.1072(2), c = 14.5341(2) A, α = 90, β = 101.4586(4), γ = 90°, V = 7741.89(17) A~3 and Z = 4. Compound 4 crystallizes in the monoclinic space group P2_1 with a = 14.4743(2), b = 12.3000(2), c = 26.5928(4) A, α = 90, β = 98.6241(5), γ = 90°, V = 4680.89(4) A~3 and Z = 4. The hexanuclear compound 3 contains a central 64-electron butterfly core with four triply bridging sulfido ligands and two bridging dppm ligands. The core of 4 consists of an open cluster of three metal atoms with two metal-metal bonds capped by two sulfido ligands and the bidentate dppm ligand bridging the open metal-metal edge and is comparable with that of 1 from which it is derived by replacing one equatorial carbonyl group from one of the exterior metal atoms of the cluster with a PPh_3 ligand.