ELECTRONIC STRUCTURES AND THERMOLYSES OF 2-TETRAZENES

Article abstract of DOI:10.1016/0040-4020(86)80015-1

The electronic structures and gas phase termolyses of the cyclic 2-tetrazenes 2 and 3 of open chain 1,1,4,4-tetramethyl-2-tetrazene (1) have been studied by photoelectron spectroscopy.While the six-membered ring compound 2 yields 1-methylmethylenamine (6) and nitrogen as fragments, the seven-membered ring compound 3 is contracted to 1,2-dimethylpyrazolidine (11).The acyclic 2-tetrazene 1 prefers disproportionation to 6 and dimethylamine (7).Based on MNDO calculations the ionization potentials of 1 - 3 were assigned to molecular orbitals.Several conformations of 2 and 3 were calculated.Compound 2 shows a rigid boat conformation with equatorial methyl groups, while 3 can occupy several conformations of similar energies.The different thermal decompositions of 1 - 3 are explained.