Il. Freriks et al., GAS-PHASE REACTIVITY OF AMBIDENT THIO-ENOLATE AND OXIMATE ANIONS, Rapid communications in mass spectrometry, 7(8), 1993, pp. 757-762
The gas-phase chemical behaviour of ambident thio-enolate anions from
thioacetaldehyde and oximate anions from acetaldoxime and acetone oxim
e has been studied using the method of Fourier-transform ion cyclotron
resonance mass spectrometry. It appears that the thio-enolate anions,
generated by an efficient base-induced E2 elimination of ethene from
ethyl vinyl sulfide, exhibit a strong preference for addition via the
sulfur rather than via the carbon nucleophilic center in the reactions
with a series of unsaturated polyfluorocarbon compounds. This preferr
ed addition via the sulfur nucleophilic center is considered to be pro
moted both by specific frontier orbital and by electrostatic interacti
ons between the reactants. Further, acetaldoxime and acetone oximate a
nions exclusively react via the oxygen nucleophilic center with the se
ries of unsaturated polyfluorocarbon compounds. Electrostatic interact
ions are held responsible for the reaction selectivity of the oximate
anions. This is in contrast with the corresponding enolate anions, for
which it is considered that the previously studied ambident chemical
behaviour is governed by specific frontier orbital interactions.