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 PPh3result in mixtures of products, among which [Cu2Ru8(CO)26]2-(5), Ru4(CO)12(CuPPh3)4(6), Ru4(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 iPrOH as a solvent and a hydrogen source.

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

M. Bortoluzzi;
2022-01-01

Abstract

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 PPh3result in mixtures of products, among which [Cu2Ru8(CO)26]2-(5), Ru4(CO)12(CuPPh3)4(6), Ru4(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 iPrOH as a solvent and a hydrogen source.
2022
61
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10278/5007600
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