The Unimolecular Chemistry of +.: a Rationale in Terms of Hydrogen-bridged Radical Cations

Article abstract of DOI:10.1002/oms.1210230512

By combining results from a variety of mass spectrometric techniques (metastable ion, collisional activation, collision-induced dissociative ionization, neutralization-reionization spectrometry and appearance energy measurements) and the classical method of isotopic labelling, a unified mechanism is proposed for the complex unimolecular chemistry of ionized 1,2-propanediol.The key intermediates involved are the stable hydrogen-bridged radical cations ^+., which were generated independently from <4-methoxy, 1-butanol>^+. (loss of C2H4) and <1-methoxyglycerol>^+. (loss of CH2O), ^+. and the related ion-dipole complex ^+..The latter species serves as the precursor for the loss of CH3^. and in this reaction the same non-ergodic behaviour is observed as in the loss of CH3^. from the ionized enol of acetone.