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Electronic Structure and Gas‐Phase Thermolysis of 2‐Tetrazenes with Acyclic or Cyclic Amino Groups Studied by Photoelectron Spectroscopy
Author(s) -
Rademacher Paul,
Heymanns Peter,
Münzenberg Ralf,
Wöll Heike,
Kowski Klaus,
Poppek Rainer
Publication year - 1994
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19941271033
Subject(s) - chemistry , imine , disproportionation , amine gas treating , x ray photoelectron spectroscopy , thermal decomposition , photoemission spectroscopy , alkyl , medicinal chemistry , spectroscopy , photochemistry , gas phase , molecular orbital , crystallography , stereochemistry , organic chemistry , molecule , catalysis , physics , nuclear magnetic resonance , quantum mechanics
The electronic structures and the gas‐phase thermolyses of the 2‐tetrazenes 2–13 have been studied by He(I) photoelectron spectroscopy. The compounds are characterized by at least three ionization potentials with energies less than 10 eV which are assigned to the molecular orbitals π 3 (HOMO), n + , π 2 , and n ‐ . In the thermolyses either the formal disproportionation products (amine and imine) of the respective aminyl radical are found, or the latter is stabilized by loss of an alkyl radical affording also an imine. Further products which can be explained by radical reactions are detected in flash vacuum pyrolyses. The tricyclic cis ‐2‐tetrazene 13 is cleaved by [2 + 2 + 2] cycloreversion. The methoxymethylsubstituted compound 8 exhibits a more complex cleavage pattern.