S. Nelsen, G. T. Cunkle, P. Gannett
May 1, 1983
Citations
0
Influential Citations
2
Citations
Journal
ChemInform
Abstract
Abstract: 2-Chloro-1,3,3-trimethyl-2-azabicyclo[2.2.2]octane [l(Cl)] was found by I3C NMR to have a ActN (-95 “C) of 7.57 (3) kcal/mol and 9-chloro-9-azabicyclo[3.3.l]nonane [4(Cl)] a ActN (+35 “C) of 14.24 (5) kcal/mol. The Eo’ for l(C1) in acetonitrile is +1.25 V vs. SCE and its vertical first ionization potential 8.10 eV. E”’ for 3,3-dimethyl-2-azabicyclo- [2.2.2]octanyl-2-oxy [2(0.)] is +OS6 V. Comparison of Eo’ values for 1(X), Z(X), and 2-azabicyclo[2.2.2]octane derivatives 3(X) and 4(X) with X = O., N=],, and C1 are made. Larger changes in Eo’ with bicyclic alkyl group changes are seen when ActN for the neutral compound is larger, and the implications of this fact are discussed. The irreversible ET values for the corresponding methylamines reflect the same trends as the alkyl groups are changed. Large changes in geometry at nitrogen frequently accompany electron loss from amino nitrogen compounds R,NX. Nitrogen prefers to be pyramidal in the neutral form but planar in the radical cation. Strain energy differences resulting from these geometrical preferences must show up in the free energy of electron