Gas phase flash pyrolysis of 3-azido-1,2,4-triazole: generation and ultraviolet photoelectron spectrum of N-cyanomethanimine

A dimer of HCN, N-cyanomethanimine 6, was prepared by flash pyrolysis (gas phase, 10−2 mbar) from 3-azido-1,2,4-triazole 1a and detected by ultraviolet photoelectron spectroscopy (HeI). Its ionization potentials were measured and the ionic states sequence proposed, with the aid of ab initio – CI (configuration interaction) calculations. The study of the MNDO potential hypersurface enabled us to propose a mechanism of the thermal reorganization of the precursor 1a. It is shown that the reaction path passes through the formation of the protomer 1b before thermal decomposition and the generation of the nitrene 2b.