SYNTHESIS OF THIOLATO HETEROMETALLIC CLUSTERS FROM THE REACTION OF OS-3(CO)(9)(MCME)(MU-H)(MU-SME) WITH GPW(CO)(3)H

Decarbonylation of triosmium methylthiolato cluster Os-3(CO)(10)(mu-H) (mu-SMe) with Me(3)NO in acetonitrile solution gave cluster Os-3(CO)(9 )(NCMe)(mu-H)(mu-SMe) (1), in which one axial CO on the non-bridged Os atom is replaced by an acetonitrile ligand. Crystal data for 2: space group P bca, a = 14.491(1), b = 16.107(5), c = 16.639(5) Angstrom, Z = 8; R(F) = 0.037, R(W) = 0.033. Treatment of 2 with CpW(C0)(3)H in re fluxing THF solution yielded two cluster compounds with formula CpWOs( 3)(CO)(11)(mu-H)(2)(mu(3)-SMe) (2) and CpWOs(3)(CO)(11)(mu-H)(2)(mu-SM e) (3) as the principle products. The first possesses a spiked-triangu lar geometry with a triply bridging thiolato ligand and the second ado pts a butterfly metal core arrangement with an edge-bridging thiolato grouping. The structure of 2 was characterized by single-crystal X-ray diffraction. Crystal data: space group P (1) over bar, a = 8.865(5), b = 8.959(3), c = 16.688(4) Angstrom, alpha = 103.49(2), beta = 93.58( 3), gamma = 113.03(4)degrees, Z = 2, R(F) = 0.034, R(W) = 0.035.