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

The reactions of [HRu3(CO)(11)](- )(1) with M(I) (M = Cu, Ag, and Au) compounds such as [Cu(CH3CN)(4)][BF4], AgNO3, and Au(Et2S)Cl afford the 2-D molecular alloy clusters [CuRu6(CO)(22)](- )(2), [AgRu6(CO)(22)](- )(3), and [AuRu5(CO)(19)](- )(4), respectively. The reactions of 2-4 with PPh3 result in mixtures of products, among which [Cu2Ru8(CO)(26)](2-) (5), Ru-4(CO)(12)(CuPPh3)(4 )(6), Ru-4(CO)(12)(AgPPh3)(4) (7), Ru(CO)(3)(PPh3)(2) (8), and HRu3(OH)-(CO)(7)(PPh3)(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 [NEt4](+) 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.

Automated summary

In this study, the reactions between [HRu3(CO)(11)](-) and Cu, Ag, and Au compounds were investigated, resulting in the formation of two-dimensional molecular alloy clusters. Additionally, various products were obtained through reactions with PPh3, and some of these compounds were isolated and characterized. The molecular structures of the compounds and the metal-metal bonding within them were determined using X-ray diffraction and density functional theory calculations. Furthermore, the [NEt4](+) salts of the compounds were tested as catalyst precursors for transfer hydrogenation reactions.