Combined Experimental and Computational Investigation of the Elementary Reaction of Ground State Atomic Carbon (C; 3Pj) with Pyridine (C5H5N; X1A1) via Ring Expansion and Ring Degradation Pathways

We explored the elementary reaction of atomic carbon (C; 3Pj) with pyridine (C5H5N; X1A1) at a collision energy of 34 ± 4 kJ mol–1 utilizing the crossed molecular beams technique. Forward-convolution fitting of the data was combined with high-level electronic structure calculations and statistical (RRKM) calculations on the triplet C6H5N potential energy surface (PES). These investigations reveal that the reaction dynamics are indirect and dominated by large range reactive impact parameters leading via barrier-less addition to the nitrogen atom and to two chemically nonequivalent “aromatic” carbon–carbon bonds forming three distinct collision complexes. At least two reaction pathways through atomic hydrogen loss were identified on the triplet surface. These channels involve multiple isomerization steps of the initial collision complexes via ring-opening and ring expansion forming an acyclic 1-ethynyl-3-isocyanoallyl radical (P1; 2A″) and a hitherto unreported seven-membered 1-aza-2-dehydrocyclohepta-2,4,6...