Preparation and structures of several complexes containing carbon-rich ligands attached to polynuclear metal carbonyls

Abstract

Several new gold-containing cluster complexes have been prepared from the reactions of gold alkynyl complexes, L n M-C x -Au(PPh3), (x = 3, 4, 6) with Ru3(CO)10(NCMe)2. The bis-cluster complex 1,4-{AuRu3(CO)9(PPh3)(μ3-C2)}2C6H4 was obtained from Ru3(CO)10(NCMe)2 and 1,4-{(Ph3P)Au(C≡C)}2C6H4. The complexes Ru3(μ-H){μ3-C2C≡C[Ru(PP)Cp′]}(CO)9 [PP = (PPh3)2, Cp′ = Cp; PP = dppe, Cp′ = Cp*] were also obtained as minor by-products and synthesised independently from Ru(C≡CC≡CH)(PP)Cp′. A reaction between Co3{μ3-CC≡CC≡CAu(PPh3)}(μ-dppm)(CO)7 and Ru3(CO)12 afforded {(Ph3P)(OC)9AuRu3}C≡CC≡CC{Co3(μ-dppm)(CO)7} 7. Related complexes AuRu3{μ3-C2C≡[M(CO)2Tp]}(CO)9(PPh3) (M = Mo 8, W 9) were obtained from {Tp(OC)2M}≡CC≡C{Au(PPh3)}, while the mixed metal cluster complexes MoM2(C2Me)(CO)8Tp (M = Ru 13, Fe 14) were obtained from M(≡CC≡CSiMe3)(CO)2Tp (M = Mo, W) with Fe2(CO)9 and Ru3(CO)12, respectively. Reactions of the Mo carbyne complex with Co2(LL)(CO)6 [LL = (CO)2, μ-dppm] or nickelocene afforded complexes 15–17 in which Co2 and Ni2 fragments, respectively, had coordinated to the C≡C triple bond. XRD structural determinations of 7, 8, 14, 16 and {Tp(OC)2W}≡CC≡CC≡{Co3(μ-dppm)(CO)7} (18-W) are reported.