Appearance energies and metastable peak shapes for methyl loss from the molecular ions of cyclohexene, methylcyclopentenes, methylenecyclopentane, bicyclo[3.1.0]hexane, and 2-methyl-1,4-pentadiene indicate that they have a common reaction pathway which produces [cyclopentenium]+ as the daughter ion at threshold.From measurements of appearance energies and from relative peak abundances and kinetic energy releases for the metastable losses of CH3• and labelled methyl from the deuterium labelled cyclic [C6H10]+• molecular ions it was concluded that: (a) H/D mixing in [cyclohexene]+• occurs in the intact ring prior to a concerted methyl extrusion; (b) [methylcyclopentenes]+• loses methyl without any H/D mixing at or near to threshold by a straight C—C cleavage, possibly via the 3-isomer. Methyl losses involving H/D mixing are preceded by ring opening which has an activation energy of ca. 1 eV. However, [cyclopentenium]+• is again the daughter ion; (c) methylenecyclopentane and bicyclo[3.1.0]hexane molecular ions isomerize to methylcyclopentenes prior to methyl loss.H/D mixing (prior to methyl loss) in the molecular ion 1,1-2H2-2-methyl-1,4-pentadiene takes place before cyclisation to methylcyclopentene.
