Abstract
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 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 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 as a σ and as a π radical.
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