Hexa- and Octanuclear Heterometallic Clusters with Copper–, Silver–, or Gold–Molybdenum Bonds and d10–d10 Interactions

Abstract

A comparative study of the reactivity of the carbonylmetalates {m}− = [MoCp(CO)3]− (Cp = η5-C5H5) and [Mo(η5-C5H4NMe2)(CO)3]− toward d10 complexes of the group 11 metals, [Cu(NCMe)4](BF4), AgBF4 and [N(n-Bu)4][AuBr2], has allowed the characterization of new heterometallic hexa- and octanuclear clusters with the same general formula [M{m}]n (M = Cu, Ag, Au). In these cyclic oligomers, the value of n depends of the coinage metal. Thus, the hexanuclear cluster [Cu3{Mo(η5-C5H4NMe2)(CO)3}3] (17) has a planar metal core, formed by a copper triangle with edge-bridging molybdenum atoms. The octanuclear “star shape” clusters [Ag4{Mo(η5-C5H4NMe2)(CO)3}4] (19) and [Au4{Mo(η5-C5H4NMe2)(CO)3}4] (21) contain a square silver or gold core, respectively, edge-bridged by molybdenum atoms. In these three clusters, the 2-D raft-type structure of their metal core, which is ν2-triangular for Cu3Mo3 and of a square-in-a-square-type for the octanuclear Ag4Mo4 and Au4Mo4 clusters, allows for d10–d10 metallophilic interactions. Th...