No / The reactions of ionised pyridazine, aminopyrazine and aminopyridine and the corresponding ¿-distonic ions are examined by a combination of tandem mass spectrometric techniques, including analysis of metastable ion (MI), collision induced dissociation and neutralisation¿reionisation mass spectra (NRMS). Further insight into the relative stability and energy barriers towards tautomerism of each ionised heterocycle with its ¿-distonic isomer is obtained by computational methods. In all these systems, both the conventional radical-cation and the ¿-distonic tautomer are stable species which exist in discrete energy wells, with a significant barrier towards their interconversion. Although each ¿-distonic ion is sufficiently stable to survive neutralisation¿reionisation, the conventional ionised heterocycle is more stable in each case. The possibility of investigating proton-transport catalysis in the tautomerism of these ionic systems is discussed.