Applications of ENDOR spectroscopy to radical cations in freon matrices. Part 2. The radical cation of 2,3‐diazabicyclo[2.2.2]oct‐2‐ene

The radical cation of 2,3‐diazabicyclo[2.2.2]oct‐2‐ene (1), generated by γ‐rays in a CF2ClCFCl2 matrix, has been fully characterized by its hyperfine data with the use of ESR, ENDOR, and TRIPLE resonance spectroscopy. The isotropic coupling constants for {article}{empty}{document}1^ -4pt .{document} are +3.14 mT for the two 14N Nuclei in the azo group, −0.336 mT for the two protons at the bridgehead C atoms, and +151 and +0.135 mT for the sets of four exo‐ and four endo‐protons, respectively. MO calculations indicate that these values are consistent with an electron removal from an orbital represented by the antibonding combination (n_) of the lone‐pair atomic orbitals at the two N atoms. The corresponding radical anion {article}{empty}{document}1^ -4pt .{document} is persistent in fluid solution and its hyperfine data, combined with MO calculations, point to an electron uptake into the antibonding π orbital (π*) of the azo group. It is, thus, reasonable to classify {article}{empty}{document}1^ +-4pt .{document} as a σ and {article}{empty}{document}1^ -4pt .{document} as a π radical.