Protonated aniline - one of the simplest nitrogen-bearing molecules - is speculated to be present within Titan's atmosphere, where it could play a role in molecular weight growth chemistry. To investigate this possibility, this paper examines the reactions of propene with distonic radical cations derived from protonated aniline. The reaction kinetics, products and branching ratios of these distonic radical cations (i.e., 2-, 3-, and 4-dehydroanilinium radical cations) are measured in the gas phase and ion-trap mass spectrometry and calculations (M06-2X/6-31G(2df,p) and G3X-K) are used to characterize each reaction. The reaction efficiencies for the 2-, 3-, and 4-dehydroanilinium radical cations are reported as 30.7 (3.1)%, 2.4 (0.5)%, and 2.1 (0.4)%, respectively (with 50% absolute accuracy). The 4- and 3-dehydroanilinium radical cations undergo addition of propene followed by (i) methyl radical loss forming ammonio styrene cations (m/z 120) and (ii) ethylene loss pathways forming the ammonio benzyl radical cation (m/z 107). The 4-dehydroanilinium reaction favours the methyl loss over ethylene loss whereas the reverse is true for 3-dehydroanilinium. In contrast, the 2-dehydroanilinium radical cation reacts with propene to purportedly form amino tropylium cation (m/z 106) by ethyl radical loss and methyl amino tropylium cation (m/z 120) by methyl radical ejection. The energies of all minima and transition states leading to predicted dissociation products are below the energy of the initial reactants providing plausible pathways at lower temperatures of Titan's atmosphere.
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