Ambident reactivity of the nitrite ion revisited

被引：46

作者：

Tishkov, AA

Schmidhammer, U

Roth, S

Riedle, E

Mayr, H

机构：

[1] Univ Munich, Dept Chem & Biochem, D-81377 Munich, Germany

[2] Univ Munich, Lehrstuhl Biomol Opt, D-80538 Munich, Germany

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2005年 / 44卷 / 29期

关键词：

HSAB principle; kinetics; Klopman-Salem equation; Kornblum's rule; nitro compounds;

D O I：

10.1002/anie.200501274

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

(Chemical Equation Presented) Lost control: The rationalization of the ambident reactivity of NO2- by the change between charge control to orbital control has to be revised. SN1-type reactions of carbocations with NO2- give kinetically controlled product mixtures only when these reactions proceed without activation energy (diffusion control). Activation-controlled SN1 alkylations are reversible and lead to the thermodynamically more stable nitro compounds. © 2005 Wiley-VCH Verlag GmbH &Co. KGaA.

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页码：4623 / 4626

页数：4

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