Hydration of Aliphatic Nitriles Catalyzed by an Osmium Polyhydride: Evidence for an Alternative Mechanism

The hexahydride OsH₆(PⁱPr₃)₂ competently catalyzes the hydration of aliphatic nitriles to amides. The main metal species under the catalytic conditions are the trihydride osmium­(IV) amidate derivatives OsH₃{κ²-N,O-[HNC­(O)­R]}­(PⁱPr₃)₂, which have been isolated and fully characterized for R = ⁱPr and ^tBu. The rate of hydration is proportional to the concentrations of the catalyst precursor, nitrile, and water. When these experimental findings and density functional theory calculations are combined, the mechanism of catalysis has been established. Complexes OsH₃{κ²-N,O-[HNC­(O)­R]}­(PⁱPr₃)₂ dissociate the carbonyl group of the chelate to afford κ¹-N-amidate derivatives, which coordinate the nitrile. The subsequent attack of an external water molecule to both the C­(sp) atom of the nitrile and the N atom of the amidate affords the amide and regenerates the κ¹-N-amidate catalysts. The attack is concerted and takes place through a cyclic six-membered transition state, which involves C_nitrile···O–H···N_amidate interactions. Before the attack, the free carbonyl group of the κ¹-N-amidate ligand fixes the water molecule in the vicinity of the C­(sp) atom of the nitrile.