Metal Acetyllde CpW(CO)₃C≡CPh and Hydride CpW(CO)₃H Complexes as Building Blocks To Prepare Tungsten-Ruthenium Heterometallic Clusters. Synthesis, Characterization, and Crystal Structure of CpWRu₃(CO)₉(μ₃−COMe)(C=CHPh), Cp₂W₂Ru₃(CO)₉[CC(Ph)C(OMe)](C=CHPh), and Cp₂W₂Ru₃(CO)₉(COMe)(C≡CPh)

The reaction of the methoxymethylidyne complex HRu₃(CO)₁₀(μ−COMe) (1) and the tungsten acetylide complex CpW(CO)₃C≡CPh in refluxing toluene produced the vinylidene complex CpWRu₃(CO)₉(μ₃− COMe)(C=CHPh) (2). The fluxionality of the Ru-CO ligands of 2 was studied by variable-temperature ¹³C NMR spectroscopy. Further reaction of 2 with the tungsten acetylide CpW(CO)₃C≡CPh gave another vinylidene complex, Cp₂W₂Ru₃(CO)₉[CC(Ph)C(OMe)](C=CHPh) (3), whereas reaction with the tungsten hydride CpW(CO)₃H produced the acetylide complex Cp₂W₂Ru₃(CO)₉(μ₃−COMe)(C≡CPh) (4). The structures of complexes 2-4 were determined by X-ray diffraction studies. Crystal data for 2: space group P2₁/n; a = 8.986 (3) Å, b = 17.577 (3) Å, c = 16.460 (2) Å,β = 94.11 (1)°, Z = 4; final R_F = 0.021 and R_w = 0.026 for 4055 reflections with I > 2σ(I). Crystal data for 3: space group P1; a = 10.356 (3) Å, b = 10.887 (1) Å, c = 18.121 (2) Å, α = 91.28 (1)°, β = 76.76 (1)°, γ = 110.34 (2)°, Z = 2; final R_F = 0.024 and R_W = 0.030 for 5571 reflections with I > 2.5σ(I). Crystal data for 4: space group P2₁/c, a = 9.850 (1) Å, b = 10.702 (1) Å, c = 30.721 (3) Å, β = 96.597 (1)°, Z = 4; final R_F = 0.064 and R_w = 0.070 for 4663 reflections with I > 2σ(I). The most striking structural feature of the Ru₃W₂ complexes 3 and 4 involves the presence of quadruply bridging vinylidene (μ₄−η²−C=CHPh) and carbonyl (μ₄−η²−CO) ligands, respectively.