Synthesis of the tetranuclear mixed-metal carbido clusters [WRu3L(CO)11(µ4-C)(µ-H)]via methoxymethylidyne clusters [WRu3L(CO)11(µ3-COMe)](L =η-C5H5 or η-C5Me5). Crystal structures of [WRu3(η-C5Me5)(CO)11(µ3-COMe)] and [WRu3(η-C5H5)(CO)11(µ4-C)(µ-H)]

Abstract

Treatment of the complex [Ru₃(CO)₁₀(µ-COMe)H] with a slight excess of [WL(CO)₃H](L =η-C₅H₅ or η-C₅Me₅) in refluxing toluene solution (45 min) produces a methoxymethylidyne complex [WRu₃L(CO)₁₁(µ₃-COMe)][L =η-C₅H₅, (4a); or η-C₅Me₅, (4b)]. Hydrogenation of (4a) and (4b) in toluene induces scission of the C–O bond, giving a unique carbido cluster [WRu₃L(CO)₁₁(µ₄-C)(µ-H)][L =η-C₅H₅, (3a); or η-C₅Me₅, (3b)]. The crystal structures of complexes (4b) and (3a) have been determined. Crystal data for (4b); space group P2₁/c, a= 8.993(2), b= 14.565(3), c= 21.090(3)Å, β= 90.66(2)°, Z= 4, R= 0.029, and R′= 0.030. Crystal data for (3a): space group Pca2₁, a= 19.685(3), b= 7.855(3), c= 14.054(3)Å, Z= 4, R= 0.033, and R′= 0.037.