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

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