Structure and Dissociation Pathways of Protonated Tetralin (1,2,3,4-Tetrahydronaphthalene).

Abstract

The infrared multiple-photon dissociation (IRMPD) spectrum of protonated tetralin (1,2,3,4-tetrahydronaphthalene, THN) has been recorded using an infrared free electron laser coupled to a Fourier transform ion cyclotron mass spectrometer. IR-induced fragmentation of the protonated parent [THN + H] +, m/z 133, yielded a single fragment ion at m/z 91. No evidence for fragment ions at m/z 131 or 132 was observed, indicating that protonated THN ejects neither atomic H nor molecular H2. Comparison of the experimental spectrum with density functional calculations (B3LYP/6-311++G(d,p)) of the two possible protonated isomers identifies a preference for the position of protonation. Possible decomposition pathways starting from both [THN + H(5)]+ and [THN + H(6)]+ are investigated. The potential energy profiles computed for these decomposition routes reveal that (1) the m/z 91 ionic product resembles the benzylium ion, but with the extra hydrogen and the methylene substituents in various ortho, meta, and para conformations around the aromatic ring and that (2) the decomposition process involving the [THN + H(6)]+ isomer is predominant, while the one involving the [THN + H(5)]+ may play a smaller role. Potential energy pathways from the initial decomposition product(s) to the benzylium and tropylium ions have also been computed. Given the relatively low barriers to these ions, it is concluded that the benzylium ion and, with sufficient activation, the tropylium ion plus neutral propene are the final products.