Synthesis of the mixed-metal clusters [Ru5RhC(CO)14(cod)Y][Y = H, Au(PEt3) or Au(PPh3); cod = cycloocta-1,5-diene]; reactions of [Ru5RhC(CO)14(cod){Au(PR3)}](R = Ph or Et) and crystal structure of [Ru5RhC(CO)14(cod){µ3-Au(PPh3)}]

Treatment of the pentaruthenium salt [N(PPh3)2]2[Ru5C(CO)14] with an excess of [Rh(Cod)2][SbF6](cod = cycloocta-1,5-diene) yielded the monoanion [Ru5RhC(CO)14(cod)]– which has been isolated as its [N(PPh3)2]+ salt 1. Reaction of the monoanion with HBF4·Et2O gave the hydrido derivative [Ru5RhH(C)(CO)14(cod)]2. Compound 1 reacted with the gold salts [Au(PPh3)]Cl and [Au(PEt3)]Cl, respectively, to yield the cluster compounds [Ru5RhC(CO)14(cod){Au(PPh3)}]3 and [Ru5RhC(CO)14(cod){Au(PEt3)}]4. Compound 3 crystallises in the triclinic space group P(no. 2) with a= 15.993(3), b= 9.728(2), c= 13.900(3)A, α= 90.29(2), β= 99.97(2), γ= 88.36(2)°. The metal core geometry consists of a central Ru5Rh octahedron with one Ru3 face capped by a µ3-Au(PPh3) fragment [Ru–Ru 2.787(1)–3.093(1); Ru–Rh 2.892(1)–2.952(1); Ru–Au 2.735(1)–3.082(1)A]. The reactions of 3 and 4 with norbornadiene, PPh3 and P(OMe)3 are reported.

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