Efficient catalytic hydration of acetonitrile to acetamide using [Os(CO) 3Cl 2] 2

• Published in: Journal of molecular catalysis. A, Chemical Chemical, 2003-09, Vol.204, p.279-285
• Main Authors: Cariati, Elena, Dragonetti, Claudia, Manassero, Luca, Roberto, Dominique, Tessore, Francesca, Lucenti, Elena
• Format: Article
• Language: English
• Subjects: Acetamide; Acetonitrile; Hydration; Hydrolysis; Osmium
• ISSN: 1381-1169; 1873-314X
• DOI: 10.1016/S1381-1169(03)00309-1

Various osmium species are able to activate acetonitrile towards nucleophilic attack by water to give acetamide. The most efficient catalyst appears to be [Os(CO) 3Cl 2] 2, which gives good yields of acetamide by working in air at 76 °C. The complex [Ru(CO) 3Cl 2] 2 is much less efficient than its osmium analogue due to its easy conversion in [Ru(CO) 2Cl 2(CH 3CN) 2] under the reaction conditions. Various osmium species (e.g. Na 2[Os 10C(CO) 24], OsCl 3· nH 2O and [Os(CO) 3Cl 2] 2) are able to activate acetonitrile towards nucleophilic attack by water to give acetamide. The most efficient catalyst appears to be [Os(CO) 3Cl 2] 2, which gives good yields of acetamide by working in air at 76 °C. An increase of the quantity of water has a positive effect on yields, a plateau being reached with a molar ratio H 2O:CH 3CN of about 7.3:1. The catalytic activity of the osmium species decreases with prolonged heating, due to the progressive partial decarbonylation of fac-tricarbonylosmium(II) species. The complex [Ru(CO) 3Cl 2] 2 is much less efficient than its osmium analogue due to its easy conversion in [Ru(CO) 2Cl 2(CH 3CN) 2] under the reaction conditions.