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

[Image: see text] The reactions of [HRu(3)(CO)(11)](−) (1) with M(I) (M = Cu, Ag, and Au) compounds such as [Cu(CH(3)CN)(4)][BF(4)], AgNO(3), and Au(Et(2)S)Cl afford the 2-D molecular alloy clusters [CuRu(6)(CO)(22)](−) (2), [AgRu(6)(CO)(22)](−) (3), and [AuRu(5)(CO)(19)](−) (4), respectively. The reactions of 2–4 with PPh(3) result in mixtures of products, among which [Cu(2)Ru(8)(CO)(26)](2–) (5), Ru(4)(CO)(12)(CuPPh(3))(4) (6), Ru(4)(CO)(12)(AgPPh(3))(4) (7), Ru(CO)(3)(PPh(3))(2) (8), and HRu(3)(OH)(CO)(7)(PPh(3))(3) (9) have been isolated and characterized. The molecular structures of 2–6 and 9 have been determined by single-crystal X-ray diffraction. The metal–metal bonding within 2–5 has been computationally investigated by density functional theory methods. In addition, the [NEt(4)](+) salts of 2–4 have been tested as catalyst precursors for transfer hydrogenation on the model substrate 4-fluoroacetophenone using (i)PrOH as a solvent and a hydrogen source.