Theoretical Investigations of Hydrolysis Mechanisms of N(SiMe 3 ) 3 .

Tris(trimethylsilyl)amine (N(SiMe 3 ) 3 ) is one of the most important intermediate products in the indirect synthesis of ammonia (NH 3 ) from nitrogen (N 2 ), which could be hydrolyzed to NH 3 under mild conditions. Herein, the hydrolysis mechanism of N(SiMe 3 ) 3 has been systematically investigated using density functional theory (DFT) with explicit combined implicit water models. Under neutral conditions, the active barrier of the hydrolysis of N(SiMe 3 ) 3 is 17.6 kcal mol -1 in water solvent. The attacking of proton to N center and OH group to the Si atom from water is decoupled for the stabilization of OH group by solvent water molecules, which lower the hydrolysis energy barriers. Furthermore, under acid conditions, N(SiMe 3 ) 3 is easily coordinated with proton to form [NH(SiMe 3 ) 3 ] + , and the energy barrier of the hydrolysis reaction could be reduced to 11.5 kcal mol -1 of the first stage, making it being promoted according to the chemical equilibrium. Thus, the results provide an explanation for the possible mechanism of the quantitative conversion of N(SiMe 3 ) 3 to NH 3 under mild conditions. The decoupled hydrolysis mechanism may play important role in other hydrolysis processes.