Comparison of Free Energy Changes for Nitrogen Inversion and Electron Loss for Some Amino Nitrogen Compounds

2-Chloro-l,3,3-trimethyl-2-azabicyclo[2.2.2]octane [1(C1)] was found by 13C NMR to have a δG‡N (-95 °C) of 7.57 (3) kcal/mol and 9-chloro-9-azabicyclo[3.3.1]nonane [4(C1)] a δG*n (+35°C) of 14.24 (5) kcal/mol. The E°’ for 1(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(O·)] is +0.56 V. Comparison of E°’ values for 1(X), 2(X), and 2-azabicyclo[2.2.2]octane derivatives 3(X) and 4(X) with X = O·, N=]2, and Cl are made. Larger changes in E°’ with bicyclic alkyl group changes are seen when δG‡N for the neutral compound is larger, and the implications of this fact are discussed. The irreversible Epox values for the corresponding methylamines reflect the same trends as the alkyl groups are changed.