Protonation of heterocyclic aromatic molecules: IR signature of the protonation site of furan and pyrrole

Protonated furan (C4H5O+, furanH(+)) and protonated pyrrole (C4H6N+, pyrroleH(+)) are generated by chemical ionization of the respective parent molecules in the cell of an FT-ICR mass spectrometer using CH5(+)/C(2)H5(+) as protonating agents. The protonation site is investigated by resonant infrared multiphoton dissociation (IRMPD) spectroscopy in the 900-1700cm(-1) fingerprint range employing the free electron laser (FEL) at the Centre Laser Infrarouge Orsay (CLIO). Comparison with quantum chemical calculations at the B3LYP/6-311G(2df, 2pd) level of theory demonstrates unambiguously that only the C. protonated isomers are observed, which correspond to the global minima on the potential energy surfaces of both protonated heterocyclic molecules. Spectroscopic features corresponding to protonation at the C beta atom or at the heteroatom are not detected. The IRMPD spectra correspond to the first spectroscopic identification of both protonated heterocyclic molecules in the gas phase. During the course of the experiments, the IRMPD spectrum of the furan radical cation (C4H4O+, furan(+)) has been detected as well. Comparison of the IR spectra of the neutral molecules with the IRMPD spectra of the radical cation and the protonated species reveals the effects of both ionization and protonation on the structural properties of these fundamental heterocyclic molecules. (C) 2007 Elsevier B.V. All rights reserved.