ELECTRONIC-STRUCTURE AND GAS-PHASE THERMOLYSIS OF 2-TETRAZENES WITH ACYCLIC OR CYCLIC AMINO-GROUPS STUDIED BY PHOTOELECTRON-SPECTROSCOPY

The electronic structures and the gas-phase thermolyses of the 2-tetra zenes 2-13 have been studied by He(I) photoelectron spectroscopy. The compounds are characterized by at least three ionization potentials wi th energies less than 10 eV which are assigned to the molecular orbita ls pi3 (HOMO), n+, pi2, and n-. In the thermolyses either the formal d isproportionation products (amine and imine) of the respective aminyl radical are found, or the latter is stabilized by loss of an alkyl rad ical affording also an imine. Further products which can be explained by radical reactions are detected in flash vacuum pyrolyses. The tricy clic cis-2-tetrazene 13 is cleaved by [2 + 2 + 2] cycloreversion. The methoxymethyl-substituted compound 8 exhibits a more complex cleavage pattern.