Azatriquinane (= 10-azatricyclo[5.2.1.01,10]decane; 1) was oxidized to its radical cation 1·+ by γ- irradiation in a CF2ClCFCl2 matrix at 77 K. A prominent feature of the ESR spectrum of 1·+ is the 14N-hyperfine anisotropy which broadens the components with M1(14N)=±1. The observed coupling constants are aN=+2.5 and aH = + 4.0 mT for the 14N nucleus and the three methine β-protons, respectively. While the aN value points to pyramidalization at the N-atom comparable to that in the radical cation of quinuclidine (= 1-azabicyclo[2.2.2]octane; 4), an eclipsing of the singly occupied orbital at this atom by the three C-Hβ bonds is indicated in view of the large aH value. Theoretical calculations on the geometry of 1·+ are in accord with the conclusions drawn from the experimental findings.
|Original language||English (US)|
|Number of pages||5|
|Journal||Helvetica Chimica Acta|
|State||Published - 1998|
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