Stereoelectronic and dynamical effects dictate nitrogen inversion during valence isomerism in benzene imine.

Benzene imine (1) ⇌ 1H-azepine (2) isomerization occurs through sequential valence and endo-exo isomerism. Quantum chemical and quasiclassical trajectory (QCT) simulations reveal the coupled reaction pathway - ring-expansion followed by N-inversion to the most stable isomer, exo-1H-azepine (Exo-2). Direct-dynamics produce a mixture of endo- and exo-1H-azepine stereoisomers and govern the endo-1H-azepine (Endo-2) ⇌ exo-1H-azepine (Exo-2) ratio. Exo-2 is computationally identified as the most stable product while Endo-2 is fleetingly stable with a survival time (S T) ∼50 fs. N-Methyl substitution exclusively results in an exo-1-methyl-1H-azepine isomer. F-substitution at the N-site increases the barrier for N-inversion and alters the preference by stabilizing Endo-2. Interestingly, the exo-1-fluoro-1H-azepine (minor product) is formed through bifurcation via non-statistical dynamics. A highly concaved Arrhenius plot for 1a → 2a highlights the influence of heavy-atom tunneling on valence isomerism, particularly at low temperatures. Heavy-atom tunneling also results in a normal N-H(D) secondary KIE above 100 K even though the increase in hybridization from sp2 to sp3 at nitrogen should cause an inverse KIE classically.