CLUSTER SYNTHESIS .26. CONDENSATION OF RU3(CO)9(MU-3-MEC2NME2)(MU-3-S) TO RU6(CO)14(MU-3-MEC2NME2)2(MU-4-S)2 AND RU6(CO)13(MU-MEC2NME2)(MU-3-MEC2NME2)(MU-4-S)2

Ru3(CO)9(μ3-MeC2NMe2)(μ3-S), 1, undergoes a sequence of decarbonylations that leads to the coupling and fusing of two triruthenium groups. The hexaruthenium compounds Ru6(CO)14(μ3-MeC2NMe2)(μ4-S)2, 2, and Ru6(CO)13(μ-MeC2NMe2)(μ3-MeC2NMe2)(μ4-S)2, 3, were obtained by decarbonylation at 97 °C. Compound 2 was converted to 3 independently by decarbonylation at 97 °C. 2 and 3 were both characterized crystallographically. Compound 2 consists of a doubly spiked electron-rich butterfly tetrahedral cluster of metal atoms held together by sulfido ligands with inverted tetrahedral geometries, two bridging ynamine ligands, and one normal and two weak ruthenium-ruthenium bonds. Compound 3 consists of a monocapped pentagonal bipyramidal cluster for six ruthenium atoms and two sulfido ligands. It contains one-edge bridging and one triply bridging ynamine ligand. Crystal data for 2: space group P21/c, a = 14.912 (5) Å, b = 11.207 (3) Å, c = 24.046 (4) Å, β = 103.75 (2)°, V = 3903 (2) Å3, Z = 4, R = 0.040, and Rw = 0.046 for 3060 reflections. For 3: space group P21/n, a = 9.564 (2) Å, b = 31.383 (5) Å, c = 11.527 (2) Å, β = 103.80 (1)°, V = 3360 (2) Å3, Z = 4, R = 0.027, and Rw = 0.028 for 2280 reflections. © 1990, American Chemical Society. All rights reserved.