2-D Molecular Alloy Ru-M (M = Cu, Ag, and Au) Carbonyl Clusters: Synthesis, Molecular Structure, Catalysis, and Computational Studies.

The reactions of [HRu(CO)] () with M(I) (M = Cu, Ag, and Au) compounds such as [Cu(CHCN)][BF], AgNO, and Au(EtS)Cl afford the 2-D molecular alloy clusters [CuRu(CO)] (), [AgRu(CO)] (), and [AuRu(CO)] (), respectively. The reactions of with PPh result in mixtures of products, among which [CuRu(CO)] (), Ru(CO)(CuPPh) (), Ru(CO)(AgPPh) (), Ru(CO)(PPh) (), and HRu(OH)(CO)(PPh) () have been isolated and characterized. The molecular structures of and have been determined by single-crystal X-ray diffraction. The metal-metal bonding within has been computationally investigated by density functional theory methods. In addition, the [NEt] salts of have been tested as catalyst precursors for transfer hydrogenation on the model substrate 4-fluoroacetophenone using PrOH as a solvent and a hydrogen source.