Formamide hydrolysis in alkaline aqueous solution: Insight from ab initio metadynamics calculations

被引：64

作者：

Blumberger, Jochen

Ensing, Bernd

Klein, Michael L.

机构：

[1] Univ Penn, Ctr Mol Modeling, Philadelphia, PA 19104 USA

[2] Univ Penn, Dept Chem, Philadelphia, PA 19104 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2006年 / 45卷 / 18期

关键词：

ab initio calculations; hydrolysis; reaction mechanisms; solvent effects; thermodynamics;

D O I：

10.1002/anie.200600283

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

What is the active nucleophile in the alkaline hydrolysis of formamide: the hydroxide ion or a water molecule in its first solvation shell? To allow the two mechanisms in question to be distinguished, a 2D free-energy surface was computed (see picture) using Car-Parrinello metadynamics simulation. The results show that direct nucleophilic attack by a hydroxide ion is the preferred mechanism. (Figure Presented). © 2006 Wiley-VCH Verlag GmbH &. Co. KGaA.

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页码：2893 / 2897

页数：5

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