Concurrent rearrangement of phenylimido and alkenyl ligands on a WRu2 metal triangle

Abstract

Thermolysis of the phenylimido cluster [WRu₂(η-C₅Me₅)(CO)₇(µ₃-NPh)(CF₃CCHCF₃)]1b in refluxing toluene yielded a hydrido–alkyne complex [WRu₂(η-C₅Me₅)(CO)₆H(µ-NPh){C₂(CF₃)₂}]4via CO elimination and alkenyl C–H activation. Treatment of 4 with CO in refluxing toluene induced the formation of a second alkenyl complex [WRu₂(η-C₅Me₅)(CO)₇(µ-NPh)(CF₃CCHCF₃)]2b containing a doubly bridging imido ligand and face-bridging alkenyl ligand. This transformation between 4 and 2b is reversible since complex 4 can be regenerated by thermolysis of 2b in toluene. Complexes 4 and 2b were also examined by single-crystal X-ray diffraction. Crystal data for 4: triclinic space group P; a= 10.332(1), b= 17.296(4), c= 18.351(2)Å, α= 110.81(1), β= 106.31(1), γ= 92.46(2)°, Z= 4; final R= 0.026, R′= 0.024 for 6445 reflections with I > 2σ(I). Crystal data for 2b: monoclinic, space group P2₁/n; a= 11.398(3), b= 22.965(6), c= 11.670(3)Å, β= 99.78(2)°, Z= 4; final R= 0.025, R′= 0.024 for 3526 reflections with I > 2σ(I).