Theoretical Study of the Double Bond Migration Mechanism with Participation of Hydroxide Ion

摘要

The prototropic isomerization of the propene molecule in the presence of hydroxide ion was studied using ab initio Hartree-Fock and M011er-Plesset second-order perturbation theory (MP2) approaches,as well as the density functional theory,in a gas-phase and dimethyl sulfoxide solution.The results obtained within Born and Onsager models as well as the self-consistent isodensity (SCIPCM) and the integral equation formalism (IEFPCM) versions of the polarizable continuum model suppose the proton migration mechanism involving formation of the intermediate complex of the allyl anion with a water molecule.This mechanism looks preferable compared with the traditional two-stage one,even in the case of methylthiopropene molelcule,which forms a markedly more stable carbanion.