Reactions of tert-butyl isocyanide with distonic radical cations

Abstract

The reactivity of tert-butyl isocyanide was examined toward representative distonic radical cations. Two distinct types of reactivity were found, that characteristic of the electrophilic and/or acidic nature of the charge site of the ion, and that characteristic of the unpaired spin at the free radical moiety. Tert-butyl isocyanide reacts with charged groups via transfer of a cyanide ion and/or abstraction of a proton, while a cyano radical is transferred to the radical site. These two types of reactivity are usually mutally exclusive due to great differences in reaction rates. Tert-Butyl isocyanide reacts preferentially at the distonic radical cation’s charge site. Reaction occurs at the radical site only if the charge site is inert, for example, by virtue of low acidity and coordinative saturation. The applicability of tert-butyl isocyanide to the study of distonic radical cations is demonstrated and insight into the structures of selected charged phenyl radicals is provided.