The amide-iminol tautomerizations of N-alkylbenzamides coordinating with metal cation were investigated by electrospray ionization tandem mass spectrometry in positive mode. The iminol selected fragments have been experimentally confirmed from the mass spectra of complexes between a specific metal cation and N-alkylbenzamides along with its analogues. The potential energy surfaces involved were theoretically profiled by invoking density functional theory calculations. The characteristic signals corresponding to a peculiar MOH loss from iminol form were further employed to estimate the promotion abilities of other metal cations on tautomerism. The substituent effects were studied and results showed that the influence of metal cations related to their electron densities and their affinity to benzamide. Except for thioamides, most amides exist mainly under their keto forms. Present study provides a solid example of amide-iminol tautomerization behavior of the stable amide in gas phase under the cooperative effect of metal cation.

Gaseous amide-iminol tautomerism of <i>N</i>-alkylbenzamide induced by the cooperative effect of metal cation

248th National Meeting (2014)

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Gaseous amide-iminol tautomerism of N-alkylbenzamide induced by the cooperative effect of metal cation