THEORETICAL-ANALYSIS OF THE ROLE OF THE SOLVENT ON THE REACTION-MECHANISMS - ONE-STEP VERSUS 2-STEP KETENE-IMINE CYCLOADDITION

被引:56
作者
ASSFELD, X
RUIZLOPEZ, MF
GONZALEZ, J
LOPEZ, R
SORDO, JA
SORDO, TL
机构
[1] UNIV OVIEDO, FAC QUIM, DEPT QUIM FIS & ANALIT, E-33006 OVIEDO, SPAIN
[2] UNIV NANCY 1, CHIM THEOR LAB, CNRS, URA 510, F-54506 VANDOEUVRE LES NANCY, FRANCE
[3] UNIV OVIEDO, INST QUIM ORGANOMET ENRIQUE MOLES, E-33071 OVIEDO, SPAIN
关键词
D O I
10.1002/jcc.540150502
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
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. (C) 1994 by John Wiley & Sons, Inc.
引用
收藏
页码:479 / 487
页数:9
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