ClH⋯O and O⋯H⋯O bonded intermediates in the dissociation of low energy methyl glycolate radical cations

Low energy methyl glycolate radical cations HOCH2C(O)OCH3+, 1, abundantly lose HCO, yielding protonated methyl formate HC(OH)OCH3+. Tandem mass spectrometry based experiments on 2H, 13C and 18O labelled isotopologues show that this loss is largely (about 75%) atom specific. Analysis of the atom connectivity in the product ions indicates that the reaction proceeds analogously to the loss of HCO and CH3CO from ionized acetol HOCH2C(O)CH3+ and …