Vacuum pyrolysis of N,N-dimethyl bicyclo[3.2.0]hepta-3,6-dien-1-amine — He I ultraviolet photoelectron spectroscopic and computational studies

The photoelectron spectra of N,N-dimethylbicyclo[3.2.0]hepta-3,6-dien-1-amine (1) and its pyrolysate were obtained using an unique ultraviolet (UV) photoelectron (PE) spectrometer interfaced with a CW CO 2 laser. Pyrolysis of 1 in the source chamber of the PE spectrometer initially generates the transient N,N-dimethylcyclohepta-1E,3Z,5Z-trien-1-amine (2) — the computed barrier is 21.5 kcal mol –1 — that isomerizes to the all-cis isomer with a …