Unveiling the reaction mechanism of the N(2D) + pyridine reaction: ring-contraction versus 7-membered ring formation channels

Despite the relevance of the reactions of the prototypical nitrogen-containing sixmembered aromatic molecule (N-heterocyclic) of pyridine (C6H5N) in environmental science, astrochemistry, planetary science, prebiotic chemistry, and material science, few experimental/theoretical studies exist on the bimolecular reactions involving pyridine and neutral atomic/molecular radicals. We report a combined experimental and theoretical study on the elementary reaction of pyridine with excited nitrogen atoms, N(2D), aimed at providing information on the primary reaction products and their branching fractions (BFs). From previous crossed molecular beam (CMB) experiments with mass-spectrometric detection and present synergistic calculations of the reactive potential energy surface (PES) and product BFs we have unveiled the reaction mechanism. It is found that the reaction proceeds via N(2D) barrierless addition to pyridine that, via bridged intermediates followed by N atom “sliding” into the ring, leads to 7-membered ring structures. They further evolve, mainly via ring-contraction mechanisms toward 5-membered ring radical products and, to a smaller extent, via H-displacement mechanisms toward 7-membered ring isomeric products and their isomers. Using the theoretical statistical estimates, an improved fit of the experimental data previously reported has been obtained leading to the following results for the dominant product channels: C4H4N (pyrrolyl) + HCN (BF = 0.61 +/- 0.20), C3H3N2 (1H-imidazolyl/1H-pyrazolyl) + C2H2 (BF = 0.11 +/- 0.06), and C5H4N2 (7-membered ring molecules or pyrrole carbonitriles) + H (BF = 0.28 +/- 0.10). The ring-contraction product channels C4H4N (pyrrolyl) + HCN, C3H3N2 (1H-imidazolyl) + C2H2, C3H3N2 (1Hpyrazolyl) + C2H2, and C5H5 (cyclopentadienyl) + N2 have statistical BFs of 0.54, 0.09, 0.11, and 0.07, respectively. Among the H-displacement channels, the cyclic-CHCHCHCHNCN + H channel and cyclic-CHCHCHCHCN2 + H are theoretically predicted to have a comparable BF (0.07 and 0.06, respectively), while the other isomeric 7-membered ring molecule + H channel has a BF or 0.03. Pyrrole-carbonitriles and 1H-ethynyl-1H-imidazole (+ H) isomeric channels have an overall BF = 0.03. Implications for the chemistry of Saturn’s moon Titan and prebiotic chemistry, as well as for understanding the N-doping of graphene or carbon nanotubes, are noted.