Preparation of tetranuclear heterometallic clusters by condensation of tungsten acetylides [W(CO)₃(C≡CR) (η-C₅H₅)] with acetylide clusters [WRu₂(CO)₈(C≡CR)L] (L = η-C₅H₅ or η-C₅Me₅, R = Ph or C₆H₄F-p). Crystal structures of [W₂Ru₂(CO)₉{CC(C₆H₄F-p)}(η-C5H5)2] and [W₂Ru₂(CO)₆(CCPh)₂(η-C5H5)(η-C₅Me₅)]

Reaction of trinuclear acetylide complexes [WRu₂(CO)₈(C≡CR) (η-C₅H₅)] with 1.5 molar equivalents [W(CO)₃(C≡CR)(η-C₅H₅)] (R = Ph Or C₆H₄F-p) in refluxing toluene produced two heterometallic cluster complexes [W₂Ru₂(CO)₉(CCRCCR)(η-C₅H ₅)₂] (R = Ph, 2a; or C₆H₄F-p, 2b) and [W₂Ru₂(CO)₆(C≡CR) ₂(η-C₅H₅)₂] (R = Ph, 3a; or C₆H₄F-p, 3b). For the analogous reaction of [WRu₂(CO)₈(C≡CPh)(η-C₅Me ₅)] And [W(CO)₃(C≡CPh)(η-C₅H₅)] only the complex [W₂Ru₂(CO)₆-(C≡CPh) ₂(η-C₅H₅)(η-C₅Me ₅)] 3c was isolated. Crystal data: 2b, space group Pbca, a = 16.237(3), b = 34.006(2), c = 13.228(3) Å, Z = 8, final R = 0.077, R′ = 0.084 for 3968 reflections with I > 2σ(I); 3c, space group P1, a = 10.202(3), b = 11.703(2), c = 16.600(3) Å, α = 87.97(1), β = 103.68(2), γ = 102.66(2)°, Z = 2, R = 0.038, R′ = 0.030 for 4714 reflections with I > 2σ(I). A plausible reaction pathway which leads to the formation of both complexes 2 and 3 is presented.