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Theoretical analysis of the role of the solvent on the reaction mechanisms: One‐step versus two‐step ketene–imine cycloaddition
Author(s) -
Assfeld X.,
Ruiz–lopez M. F.,
Gonzalez J.,
Lopez R.,
Sordo J. A.,
Sordo T. L.
Publication year - 1994
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.540150502
Subject(s) - supermolecule , chemistry , ketene , cycloaddition , solvation , computational chemistry , imine , ab initio , multipole expansion , solvent effects , reaction mechanism , basis set , solvent , molecule , density functional theory , organic chemistry , physics , quantum mechanics , catalysis
The effect of correlation energy, basis set size, zero‐point energy (ZPE) correction, and solvation on the reaction mechanism of the ketene–imine cycloaddition reaction has been investigated. The electrostatic solvent effect was studied with a self‐consistent reaction field method in which the solvation energy is obtained using a multipole expansion of the molecular charge distribution. The ab initio results have been analyzed by means of a theoretical method based on the expansion of the MOs of the supermolecule in terms of those of the reactants and the performance of the configuration analysis. In gas phase, due to the correlation energy and/or the ZPE corrections, the reaction is predicted to be a one‐step process. In solution, the stabilization of the charge‐transferred configurations results in the occurrence of a very stable, Zwitterionic intermediate giving a two‐step mechanism. © 1994 by John Wiley & Sons, Inc.