P. Heymanns, P. Rademacher
1986
Citations
0
Influential Citations
12
Citations
Journal
Tetrahedron
Abstract
Abstract The electronic structures and gas phase thermolyses of the cyclic 2-tetrazenes 2 and 3 and 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 tonization 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 similiar energies. The different thermal decompositions of 1 – 3 are explained.