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Inorg Chem. 2013 Jun 17;52(12):7068-77. doi: 10.1021/ic400602y. Epub 2013 Jun 3.

Heterometallic derivatives of the unsaturated ditungsten hydride [W2(η(5)-C5H5)2(H)(μ-PCy2)(CO)2].

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Departamento de Química Orgánica e Inorgánica/IUQOEM, Universidad de Oviedo, E-33071 Oviedo, Spain.


The title complex reacted with different transition-metal (M) complexes to give heterometallic clusters with W2M and W2M2 metal cores. The reaction with [Fe2(CO)9] in THF at room temperature gave a mixture of the heterodinuclear compound [FeWCp(μ-PCy2)(CO)6] and the tetrahedral clusters [Fe2W2Cp2(μ3-H)(μ-PCy2)(CO)8] (W-W = 2.704(1) Å) and [Fe2W2Cp2(μ-H)(μ-PCy2)(μ-CO)(CO)8] (W-W = 3.058(5) Å). In contrast, its reaction with [Ru3(CO)12] under ultraviolet-visible (UV-Vis) irradiation gave only the heterodinuclear complex [RuWCp(μ-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(μ-H)(μ-PCy2)(CO)4], except in the reaction with [W(CO)6], the latter also yielding the expected 46-electron cluster [W3Cp2(μ3-H)(μ-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(μ-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·PPh3, to give the tetranuclear cluster [Cu2W2Cp2(μ-H)3(μ-PCy2)(CO)2(PPh3)2], which exists in solution as an equilibrium mixture of two isomers.


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