Synthesis of New Thiol Derivatives of Os3(CO)12; Crystal Structure of HOs3(CO)10(SBut)

The clusters [Os3(CO) 10(/z-H) {/z-SC(CH3)3} ] (1) and [Os3(CO) to(/z-H) {p-SCeHH } ] (2) have been synthesized by addition of the
appropriate thiol RSH (R ffi C(CH3)3, CeHH) to [Os3(CO) it (NCMe) ] or [Os3(CO) io(NCMe)2] in dichloromethane. Clusters 1 and 2
have been characterized by 1R, NMR, mass speetromet~, and, in the case of 1, X-ray crystallography. Compound I crystallizes in space group
P2~/n (affi9.507(1), bffi 12.860(1), cffi 17.838(3) A, flffi99.77(1) °, Zffi4). The molecule conforms to an idealized C, symmetry. The
bond distances in the osmium triangle average 2.860 A; there is no significant elongation of the Os-Os edge in I that is bridged by the hydride
and the thiolate moiety.