AB-INITIO ANALYSIS OF WATER-ASSISTED REACTION-MECHANISMS IN AMIDE HYDROLYSIS

被引：208

作者：

ANTONCZAK, S ^{[1
]}

RUIZLOPEZ, MF ^{[1
]}

RIVAIL, JL ^{[1
]}

机构：

[1] UNIV NANCY 1, CHIM THEOR LAB, CNRS, URA 510, F-54506 VANDOEUVRE LES NANCY, FRANCE

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1994年 / 116卷 / 09期

关键词：

D O I：

10.1021/ja00088a030

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The water-assisted hydrolysis of formamide has been studied at the MP3/6-31G**//3-21G ab initio level for neutral and H3O+-promoted processes. The computations predict an important catalytic effect through O-protonation, in agreement with previous results for the nonassisted reaction. Assistance by a water molecule lowers the free energy barriers of the neutral and the acid-promoted reactions, but the effect is especially large in the second case. The influence of electrostatic interactions with the bulk is discussed using a continuum model to represent the liquid. Substantial modifications of the transition-state geometries are predicted, but the average change in the activation barriers is rather small.

引用

页码：3912 / 3921

页数：10

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