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Theoretical study of the double bond migration mechanism with participation of hydroxide ion
Author(s) -
Kobychev Vladimir B.,
Vitkovskaya Nadezhda M.,
Trofimov Boris A.
Publication year - 2004
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.20092
Subject(s) - mechanism (biology) , hydroxide , ion , chemistry , bond , double bond , computational chemistry , chemical physics , inorganic chemistry , physics , polymer chemistry , business , organic chemistry , quantum mechanics , finance
The prototropic isomerization of the propene molecule in the presence of hydroxide ion was studied using ab initio Hartree–Fock and Møller–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. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2004