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Small nitrogen containing heteroaromatics are fundamental building blocks for many biological molecules, including the DNA nucleotides. Pyridine, as a prototypical N-heteroaromatic, has been implicated in the chemical evolution of many extraterrestrial environments, including the atmosphere of Titan. This paper reports on the gas-phase ion-molecule reactions of the three dehydro-N-pyridinium radical cation isomers with propene. Photodissociation ion-trap mass spectrometry experiments are used to measure product branching ratios and reaction kinetics. Reaction efficiencies for 2-dehydro-N-pyridinium, 3-dehydro-N-pyridinium and 4-dehydro-N-pyridinium with propene are 70%, 47% and 41%, respectively. The m/z 106 channel is the major product channel across all cases and assigned 2-, 3-, and 4-vinylpyridinium for each reaction. The m/z 93 channel is also significant and assigned the 2-, 3-, and 4-N-protonated-picolyl radical cation for each case. H-Abstraction from propene is not competitive under experimental conditions. Potential energy schemes, at the M06-2X/6-31(2df,p) level of theory and basis set, are described to assist in rationalising observed product branching ratios and elucidating possible reaction mechanisms. Reaction barriers to the production of vinylpyridinium (m/z 106) + CH 3 are the lowest identified for the 3- and 4-dehydro-N-pyridinium reactions, in support of the observed dominance of the m/z 106 ion signal. Ethylene loss via ring-mediated H-transfer along the propyl group is found to be the lowest energy pathway for the 2-dehydro-N-pyridinium reaction, suggesting a preference toward m/z 93 (N-protonated-picolyl radical cation) over the experimentally observed products. Entropic bottle-necks along the m/z 93 pathway however, associated with ring-mediated H-atom transfer, are responsible for the dominance of m/z 106 in the 2-dehydro-N-pyridinium + propene reaction. For all three isomers, computed barriers for all observed reaction channels were below the entrance channel, suggesting these reactions can contribute to molecular weight growth in extraterrestrial environments with accelerated reaction rates in low temperature regions of space.

Highly efficient gas-phase reactivity of protonated pyridine radicals with propene