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

Benzene imine (1) ⇌ 1 H -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 -1 H -azepine (Exo-2). Direct-dynamics produce a mixture of endo - and exo -1 H -azepine stereoisomers and govern the endo -1 H -azepine (Endo-2) ⇌ exo -1 H -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-1 H -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-1 H -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 sp 2 to sp 3 at nitrogen should cause an inverse KIE classically.