Ionized benzonitrile and its distonic isomers in the gas phase

The dehydrobenzonitrilium distonic radical cations a-c, isomers of benzonit rile radical cation d, were prepared by collisional dehalogenation of proto nated halogenobenzonitriles and characterized by tandem mass spectrometry ( MS/MS/MS experiments and ion-molecule reactions) making use of a hybrid mas s spectrometer of sector-quadrupole-sector configuration. These experimenta l results were further supported by density functional theory calculations at the B3LYP/6-311++G(3df,2p) level, indicating that although the distonic ions are less stable than ion d by ca. 45-50 kJ mol(-1), they are protected against isomerization by relatively large energy barriers. Relative energi es of benzonitrile and its isomers as well as their proton affinities and i onization energies were also evaluated. N-protonation in benzonitrile is ab out 120 kJ mol(-1) more exothermic than ring protonation.