Tricyclopropylamine and Its Radical Cation.
A surprisingly high first vertical ionization energy (8.44 eV) and an unusually high oxidation potential are exibited by tricyclopropylamine (1)-in sharp contrast to triisopropylamine. These are attributed to the near-tetrahedral geometry of 1 at the N atom and the perpendicular orientation-with respect to the N-orbital axis-of the cyclopropyl groups. gamma-Irradiation of 1 led to the radical cation 1(.)(+), which, in accord with computations, has a planar C(3h)-symmetrical structure. The EPR-spectroscopic and computational results disclose a dramatic, previously not reported, conformational change on going from 1 to 1(.)(+).
de Meijere A
Institut für Organische Chemie der Universität, Tammannstrasse 2, D-37077 Göttingen (Germany).
Chaplinski
V
Winsel
H
Kusnetsov
MA
Rademacher
P
Boese
R
Haumann
T
Traetteberg
M
Schleyer
Pv
Zywietz
T
Jiao
H
Merstetter
P
Gerson
F