Under an atmosphere of carbon monoxide, HOs3(CO)10(μ-SPh) (I) loses benzene when irradiated to form the new cluster compound Os3(CO)9(μ3-CO)(μ3-S) (II). II was characterized by a single-crystal X-ray diffraction analysis: space group P1, No. 2, a = 6.912 (2) Å, b = 9.500 (3) Å, c = 13.235 (6) Å, α = 82.63 (3)°, β = 87.43 (3)°, Γ = 72.30 (3)°, V = 821.1 (6) Å3, Z = 2, ρcelcd = 3.57 g/cm3. The structure was solved by the heavy-atom method and refined (2258 reflections, F2 ≥ 3.0σ(F2)) by full-matrix least-squares to the final residuals R1 = 0.056 and R2 = 0.069. The molecular structure of II consists of a triangular cluster of three osmium atoms containing a triply bridging sulfido ligand on one threefold face of the cluster and a triply bridging carbonyl ligand on the opposite threefold face. Each osmium atom contains three linear terminal carbonyl ligands. Two Os-Os separations, 2.826 (1) and 2.825 (1) Å, are slightly shorter than the third, 2.840 (1) Å. In the presence of the reagents H2, H2S, COS, and CS2, I loses both benzene and carbon monoxide when irradiated and yields the products H2Os3(CO)9(μ3-S) (IV), H2Os3(CO)8(μ3-S)2 (V), Os3(CO)9(μ3-S)2 (VI), and Os3(CO)3CS(μ3-S)2 (VII), respectively. In the absence of a reagent the hexaosmium disulfido cluster, Os6(CO)17(μ4-S)2 (III), is formed. Compounds III, IV, and V were also obtained by the photodecarbonylation of II in the presence of the appropriate reagent. It is proposed that an unsaturated intermediate such as Os3(CO)9(μ3-S) is traversed in the photoreactions of both I and II.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry