A comparison between theoretical and experimental models of electrophilicity and nucleophilicity

被引：67

作者：

Chamorro, Eduardo ^{[1
]}

Duque-Norena, Mario ^{[1
]}

Perez, Patricia ^{[1
]}

机构：

[1] Univ Andres Bello, Fac Ecol & Recursos Nat, Dept Ciencias Quim, Lab Quim Teor, Santiago 8370146, Chile

来源：

JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM | 2009年 / 896卷 / 1-3期

关键词：

Nucleophilicity; Electrophilicity; DFT; Scales; DENSITY-FUNCTIONAL THEORY; DESCRIBING CHEMICAL-REACTIONS; REACTIVITY-SELECTIVITY PRINCIPLE; DIELS-ALDER REACTIONS; LINEAR FREE-ENERGY; QUANTITATIVE CHARACTERIZATION; VARIATIONAL-PRINCIPLES; DIARYLCARBENIUM IONS; AMBIDENT REACTIVITY; LOCAL ELECTROPHILICITY;

D O I：

10.1016/j.theochem.2008.11.009

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：

Four different theoretical models of electrophilicity and nucleophilicity has been discussed in the light of experimental available evidence for a series of 20 benzhydrylium ions taken as reference electrophilic systems and 16 primary and secondary amines as nucleophilic systems. It is shown that the theoretical scales are linearly related to the well-known experimental ones based on the electrophilicity (E) and nucleophilicity (N and s) parameters derived by Mayr from the rate constants k(20 degrees C) associated to general electrophile-nucleophile combinations, log k(20 degrees C) = s(N + E). (C) 2008 Elsevier B,V. All rights reserved.

引用

页码：73 / 79

页数：7

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