Hydration of carbonyl compounds, an analysis in terms of multidimensional marcus theory

被引：118

作者：

Guthrie, JP ^{[1
]}

机构：

[1] Univ Western Ontario, Dept Chem, London, ON N6A 5B7, Canada

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2000年 / 122卷 / 23期

关键词：

D O I：

10.1021/ja992992i

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Rate constants for base-catalyzed, uncatalyzed, and acid-catalyzed additions of water to 50 compounds (aldehydes, ketones, esters, thioesters, and amides) have been calculated using Multidimensional Marcus Theory. For all of these reactions except hydroxide addition to reactive aldehydes a single average value of the intrinsic barrier (8.51 kcal/mol) can be used to give calculated values within 1 kcal/mol (root-mean-square error) of the observed values. For the addition of hydroxide to reactive aldehydes it is necessary to use an intrinsic barrier linearly related to the equilibrium constant for hydroxide addition. The work term in Marcus Theory is approximated by a detailed model of the solvation and statistical cost of bringing reactants together.

引用

页码：5529 / 5538

页数：10

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