Ambident Reactivity of the Nitrite Ion Revisited


  • This research was supported by the Alexander von Humboldt Foundation (stipend to A.A.T.) and the Deutsche Forschungsgemeinschaft.


original image

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.