Preparation of tetranuclear heterometallic clusters by condensation of tungsten acetylides [W(CO)3(CCR)(η-C5H5)] with acetylide clusters [WRu2(CO)8(CCR)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)]

Abstract

Reaction of Trinuclear Acetylide Complexes [WRu₂(CO)₈(CCR)(η-C₅H₅)] with 1.5 molar equivalents [W(CO)₃(CCR)(η-C₅H₅)](R = Ph Or C₆H₄F-P) in refluxing toluene produced two heterometallic cluster complexes [W₂Ru₂(Co)₉(CCRCCR)(η-C₅H₅)₂](R = Ph, 2a; or C₆H₄F-p, 2b) and [W₂Ru₂(CO)₆(CCR)₂(η-C₅H₅)₂](R = Ph, 3a; or C₆H₄F-p, 3b). For the analogous reaction of [WRu₂(CO)₈(CCPh)(η-C₅Me₅)] And [W(CO)₃(CCPh)(η-C₅H₅)] only the complex [W₂Ru₂(CO)₆-(CCPh)₂(η-C₅H₅)(η-C₅Me₅)]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 P, 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.