Structural characterization and regiochemical differentiation of alpha-cyanoethylindole isomers in the gas phase

Mass spectrometry and tandem mass spectrometry techniques have been used to study the gas phase ion chemistry of isomeric alpha-cyanoethylindoles obtained by photochemical reactions. Both the fragmentation reactions occurring in the ion source, as well as metastable decompositions produced by the molecular and selected fragment ions, have allowed us to structurally characterize and differentiate each isomer from the others. The experiments, carried out also on deuterium labeled analogs, have shown the role exerted by the alpha-cyanoethyl substituent and by its position at the indolic ring on gas phase reactions that resulted to be distinctive and selective for each isomer. Ab initio theoretical calculations have been used to evaluate the stability and chemico-physical properties of different ion structures.