104463-65-2Relevant academic research and scientific papers
Formation of tungsten-triosmium clusters. Crystal structure and reactivity of (η5-C5H5)WOs3(CO) 12(μ3-CC6H4CH 3)(μ-H)2
Chi, Yun,Shapley, John R.,Churchill, Melvyn Rowen,Li, Yong-Ji
, p. 4165 - 4170 (2008/10/08)
Previous studies have identified three mixed-metal clusters (1-3) as the major products from the reaction of CpW(CO)2(CTol) (Cp = η5-C5H5; Tol = p-C6H4CH3) and H2Os3(CO)10. A fourth, minor, product has been isolated and identified spectroscopically as CpWOs3(CO)12(μ3-CTol)(μ-H)2 (4). Complex 4 crystallizes in the centrosymmetric monoclinic space group P21/n with a = 12.531 (3) A?, b = 11.007 (2) A?, c = 21.733 (4) A?, β = 105.78(2)°, V = 2884.6 (11) A?3, and Z = 4. Diffraction data (Mo Kα, 2θ = 4-45°) were collected on a Syntex P21 automated diffractometer, and the structure was refined to RF = 6.2% for 3014 data with |Fo| > 3.0σ(|Fo|). The molecule contains a triangular triosmium core (Os(1)-Os(2) = 2.912 (1) A?, Os(2)-Os(3) = 2.875 (1) A?, Os(3)-Os(1) = 2.835 (1) A?) in which the two longer distances are believed to be associated with bridging hydride ligands; in addition, the triosmium system is capped by an asymmetrically triply bridging μ3-CTol ligand (Os(1)-C(06) = 2.184 (20) A?, Os(2)-C(06) = 2.051 (19) A?, Os(3)-C(06) = 2.025 (20) A?) and Os(1) is linked to a pendant CpW(CO)3 fragment (Os(1)-W = 3.097 (1) A?). In refluxing toluene complex 4 eliminates CpW(CO)3H and reacts with H2 or CO to form H3Os3(CO)9(μ3-CTol) (5) or HOs3(CO)10(μ3-CTol) (6), respectively. The related reaction of 4 with CpW(CO)2(CTol) provides CpWOs3(CO)10(μ3-CTol)2H (3), which implicates 4 as an intermediate in the previous synthesis of 3. The reaction of CpW(CO)2(CTol) with D2Os3(CO)10 leads to a partially modified product distribution that strongly favors the acyl complex (1-d2) at the expense of deuterated 3 + 4. This is interpreted in terms of linked pathways for forming 1 and 4 but a separate pathway for forming 2.
