Synthesis of new thiol derivatives of [Os-3(CO)(12)]; crystal structure of [Os-3(CO)(10)(mu-H){mu-SC(CH3)(3)}]

The clusters [Os-3(CO)(10)(mu-H){mu-SC(CH3)(3)}] (1) and [Os-3(CO)(10)(mu-H){mu-SC6H11}] (2) have been synthesized by addition of the appropriate thiol RSH (R=C(CH3)(3), C6H11 to [Os-3(CO)(11)NCMe)] or [Os-3(CO)(10)(NCMe)(2)] in dichloromethane. Clusters 1 and 2 have been characterized by IR, NMR, mass spectrometry and, in the case of 1, X-ray crystallography. Compound 1 crystallizes in space group P2(1)/n (a=9.507(1), b=12.860(1), c=17.838(3) Angstrom, beta=99.77(1)degrees, Z=4). The molecule conforms to an idealized C-s symmetry. The bond distances in the osmium triangle average 2.860 Angstrom; there is no significant elongation of the Os-Os edge in 1 that is bridged by the hydride and the thiolate moiety.