Author:

Keywords:

Science & Technology, Physical Sciences, Chemistry, Physical, Chemistry, 0306 Physical Chemistry (incl. Structural), 0307 Theoretical and Computational Chemistry, 3406 Physical chemistry, 3407 Theoretical and computational chemistry

Abstract:

The reaction pathway for the hydration of the ketenimine CH2CNH by H2O and (H2O)2 has been investigated by ab initio methods using STO-3G and 4-31G basis sets, optimized geometries of stationary points being determined by the gradient method. The preferred reaction is with the water dimer which, although it enters the transition state correctly oriented for proton transfer to the β-carbon, does not actually transfer this proton until after the transition state. The reaction is calculated (4-31G) to have an activation barrier of 22 kcal/mole, most of which arises due to the deformation of ketenimine and water dimer. The reaction with water monomer is far less favoured (activation barrier 67 kcal/mole using the same basis set). © 1983.