Heterometallic Derivatives of the Unsaturated Ditungsten Hydride [W2(η5-C5H5)2(H)(μ-PCy2)(CO)2]

The title complex reacted with different transition-metal (M) complexes to give heterometallic clusters with W2M and W2M2 metal cores. The reaction with [Fe-2(CO)(9)] in THF at room temperature gave a mixture of the heterodinuclear compound [FeWCp(mu-PCy2)(CO)(6)] and the tetrahedral clusters [Fe2W2Cp2(mu(3)-H)(mu-PCy2)(CO)(8)] (W-W = 2.704(1) angstrom) and [Fe2W2Cp2(mu-H)(mu-PCy2)(mu-CO)(CO)(8)] (W-W = 3.058(5) angstrom). In contrast, its reaction with [Ru-3(CO)(12)] under ultraviolet-visible (UV-Vis) irradiation gave only the heterodinuclear complex [RuWCp(mu-PCy2)(CO)(6)]. The title complex also reacted readily with [M(CO)(6)] (M = Cr, Mo, W) in toluene solution under UV-Vis irradiation, but the main product was the known tetracarbonyl complex [W2Cp2(mu-H)(mu-PCy2)(CO)(4)], except in the reaction with [W(CO)(6)], the latter also yielding the expected 46-electron cluster [W3Cp2(mu(3)-H)(mu-PCy2)(CO)(7)] in 40% yield. The title complex reacted under visible-UV irradiation with different metal metal bonded dimers in toluene solution, but only with [Ru2Cp2(CO)(4)] an heterometallic cluster was obtained, with composition [RuW2Cp3(mu-PCy2)(CO)(4)]. Its reaction with the tetrahydroborate complex [Cu(BH4)(PPh3)(2)] led to the insertion of two CuH(PPh3) fragments and release of BH3 center dot PPh3, to give the tetranuclear cluster [Cu2W2Cp2(mu-H)(3)(mu-PCy2)(CO)(2)(PPh3)(2)], which exists in solution as an equilibrium mixture of two isomers.