Theoretical studies on the transition-state imbalance in malononitrile anion-forming reactions in the gas phase and in water

摘要

Semicempirical MO theoretical studies were carried out on the nucleophilic addition of phenoxide nucleophiles to 1,1-dicyano-2-arylethenes in the gas phase and in water using the AM1 method and the Cramer-Truhlar solvation model SM2.1.The gas-phase α~n and βn values are 0.81 and 0.65, respectively, leading to the positive imbalance of I=0.16; the electric polarization and dispersion interactions of water incorporated in the SM2.1 model reduce both the α~n and β~n values to 0.61 and 0.36, giving I=0.25.