Inorganic Chemistry, Vol.49, No.5, 2372-2382, 2010
Heterometallic Chains and Clusters with Gold-Transition Metal Bonds: Synthesis and Interconversion
Anionic, metal-metal bonded heterotrinuclear chain complexes of the type {M{MoCp(CO)(3)}(2)(-) with M = Cu(I), Ag(I), and Au(I) have been prepared by reaction between a d(10) metal precursor complex and the carbonylmetalate [MoCP(CO)(3)](-). These complexes have been structurally characterized by X-ray diffraction and used as precursors to neutral 2-D hexa- or octanuclear mixed-metal clusters of the general formula [MMoCP(CO)(3)](n) (M = Cu, n = 3; M = Ag or Au, n = 4), which are characterized by a central core constituted of interacting d(10) metal ions, surrounded by the molybdenum atoms. When M = Cu, the six metal atoms form a nu(2)-triangular core whereas when M = Ag or Au, a nu(2)-square structure is observed for the octanuclear metal core. It is shown in the case of M = Cu and Ag that interconversion between the metal chain complexes of stoichiometry M[m](2) and the clusters {M[m]}(n) is possible, and the position of the equilibrium depends solely on the respective stoichiometry of the reagents. The new nu(2)-square, octanuclear, trimetallic complexes [CuAg3{MoCp(CO)(3)}(4)] (7) and [CuAu3(MoCP(CO)(3)}(4)] (8) have also been obtained and characterized in the solid-state by X-ray diffraction, as well as the unexpected double pentanuclear complex [{Na(dme)}{Cu-2[MoCp(CO)(3)](3)}](2) (9).