Reactivity of 2,6-Lutidine/BR3 and Pyridine/BR3 Lewis Pairs (R = F, Me, C6F5): A Density Functional Study

被引：20

作者：

Wu, Dongling ^{[1
]}

Jia, Dianzeng ^{[1
]}

Liu, Lang ^{[1
]}

Zhang, Li ^{[1
]}

Guo, Jixi ^{[1
]}

机构：

[1] Xinjiang Univ, Inst Appl Chem, Urumqi 830046, Peoples R China

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2010年 / 114卷 / 43期

基金：

中国国家自然科学基金;

关键词：

HETEROLYTIC DIHYDROGEN ACTIVATION; FREE CATALYTIC-HYDROGENATION; CHEMICAL-REACTIVITY; INTERMOLECULAR REACTIVITY; H-2; ACTIVATION; IMINES; BORANE; DESCRIPTOR; MECHANISM; PHOSPHINES;

D O I：

10.1021/jp105000x

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The reactivity of 2,6-lutidine/BR3 and pyridine/BR3 Lewis pairs (R = F, Me, C6F5) is investigated in detail by quantum chemical calculations. The observed reactivity difference of these pairs is interpreted in terms of the existence of a "frustrated complex" on the potential energy curve for coordination of Lewis acid and base, the profiles of local reactivity descriptors with respect to the bond distance between acid and base centers, and the thermodynamic/kinetic properties of the heterolytic dihydrogen cleavage reaction. The calculated results are shown to account well for the observed reactivity of these Lewis pairs.

引用

页码：11738 / 11745

页数：8

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