Ambident Reactivity of the Nitrite Ion Revisited

Abstract

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. Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2005/z501274_s.pdf or from the author. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.