A Comparison of Density-Functional Theory and Hartree-Fock Modeling of Organolithium Equilibria

被引：6

作者：

Streitwieser, Andrew ^{[1
]}

Leong, Yew Hung ^{[1
]}

机构：

[1] Univ Calif Berkeley, Dept Chem, Berkeley, CA 94720 USA

来源：

HELVETICA CHIMICA ACTA | 2012年 / 95卷 / 10期

基金：

美国国家科学基金会;

关键词：

Ion pair acidity; Isodesmic equation; Ab initio calculations; Density-functional theory (DFT); Microsolvation; ION-PAIR ACIDITIES; LITHIUM ENOLATE; CARBON ACIDITY; AGGREGATION; ALKYLATION; PERFORMANCE; REACTIVITY;

D O I：

10.1002/hlca.201200424

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Experimental values for a number of organolithium equilibria in THF solution expressed as pK values are compared with computational results at several theory levels. Solvation effects are considered only by coordination of lithium with two THF molecules. Best results are obtained with the hybrid density-functional method mPW1PW91, which gives satisfactory results over a range of almost 40 pK units, but explicit thermal corrections to 25 degrees are required.

引用

页码：1976 / 1984

页数：9

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