Characterization of five [C4H7O]+ Ion structures. Fragmentation of the 2‐pentanone molecular ion

Abstract

AbstractThe [C4H70]+ ions [CH2CHC(OH)CH3]+ (1), [CH3CHCHC(OH)H]+ (2), [CH2C(CH3)C(OH)H]+ (3), [Ch3CH2CH2CO]+ (4) and [(CH3)2CHCO]+ (5) have been characterized by their collision‐induced dissociation (CID) mass spectra and charge stripping mass spectra. The ions 1–3 were prepared by gas phase protonation of the relevant carbonyl compounds while 4 and 5 were prepared by dissociative electron impact ionization of the appropriate carbonyl compounds. Only 2 and 3 give similar spectra and are difficult to distinguish from each other; the remaining ions can be readily characterized by either their CID mass spectra or their charge stripping mass spectra. The 2‐pentanone molecular ion fragments by loss of the C(1) methyl and the C(5) methyl in the ratio 60:40 for metastable ions; at higher internal energies loss of the C(1) methyl becomes more favoured. Metastable ion characteristics, CID mass spectra and charge stripping mass spectra all show that loss of the C(1) methyl leads to formation of the acyl ion 4, while loss of the C(5) methyl leads to formation of protonated vinyl methyl ketone (1). These results are in agreement with the previously proposed potential energy diagram for the [C5H10O]+˙ system.