Ionized benzonitrile and its distonic isomers in the gas phase
Flammang, R × Barbieux-Flammang, M Gualano, E Gerbaux, P Le, HT Nguyen, Minh Tho Turecek, F Vivekananda, S #
AMER CHEMICAL SOC
Journal of Physical Chemistry A vol:105 issue:37 pages:8579-8587
date:Univ Mons, Organ Chem Lab, B-7000 Mons, Belgium; Univ Leuven, Dept Chem, B-3001 Louvain, Belgium; Univ Washington, Dept Chem, Seattle, WA 98195 USA
The dehydrobenzonitrilium distonic radical cations a-c, isomers of benzonitrile radical cation d, were prepared by collisional dehalogenation of protonated halogenobenzonitriles and characterized by tandem mass spectrometry (MS/MS/MS experiments and ion-molecule reactions) making use of a hybrid mass spectrometer of sector-quadrupole-sector configuration. These experimental 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 energies of benzonitrile and its isomers as well as their proton affinities and ionization energies were also evaluated. N-protonation in benzonitrile is about 120 kJ mol(-1) more exothermic than ring protonation.