Gjc. Paul et al., FAST-ATOM-BOMBARDMENT OF THE CYCLIC ACETALS - EVIDENCE INDICATING THEPREDOMINANT INVOLVEMENT OF CONDENSED-PHASE PROCESSES IN IONIZATION, Journal of the American Society for Mass Spectrometry, 4(6), 1993, pp. 493-503
A series of cyclic acetals, the 2-phenyl-1,3-dioxolanes, and their deu
terated analogues were studied by electron ionization (EI), chemical i
onization (CI), and fast-atom bombardment (FAB) mass spectrometry to g
ain insight into the primary ionization processes for these compounds
in FAB/liquid secondary ion mass spectrometry. Comparison of EI and CI
data with that of FAB led to the conclusion that the predominant [M -
H]+ ion observed in FAB for the nondeuterated cyclic acetals cannot t
o a large extent be rationalized in thermodynamic terms by known gas-p
hase ion-molecule reactions. Instead, a condensed-phase model in which
the, multicharged transition state for hydride abstraction is better
solvated than the transition state for proton transfer appears to be a
plausible explanation for the FAB data obtained for the nonlabeled cy
clic acetals; however, this explanation is not entirely sufficient to
rationalize the FAB data for the deuterated cyclic acetals. For these
compounds, a dramatic time dependence of protonation versus hydride ab
straction is observed that suggests that beam-induced reactive species
are responsible for hydride abstraction in the condensed phase. This
time dependence can be interpreted in terms of a buildup of highly rea
ctive beam-induced species in the bulk of solution. Comparison of the
results obtained for deuterated acetals with different surface activit
ies support this hypothesis.