Distonic isomerisations of imine radical cations: aspects of the reactivity of heteroatomic subunits damaged by ionising radiation

Abstract

Radical cations have been prepared by exposure of imines, PhCHNR, to ionising radiation in a fluorotrichloromethane matrix at 77 K, and studied by EPR spectroscopy. They are found to rearrange mainly via a 5-centre transition state in which intramolecular H-atom transfer occurs from the alkyl chain (R) to the initially ionised nitrogen atom, yielding radicals of the general type PhCHNH⁺–C–C–C.