Pyramidal inversion in the cyclic amine aziridine is significantly more difficult than i...

Pyramidal inversion in the cyclic amine aziridine is significantly more difficult than inversion in an acyclic amine, for example, requiring 80 kJ/mol versus 23 kJ/mol in dimethylamine according to HF/6-31G* calculations. One plausible explanation is that the transition state for inversion needs to incorporate a planar trigonal nitrogen center, which is obviously more difficult to achieve in aziridine, where one bond angle is constrained to a value of around 60°, than it is in dimethylamine. Such an interpretation suggests that the barriers to inversion in the corresponding four- and fivemembered ring amines (azetidine and pyrrolidine) should also be larger than normal and that the inversion barrier in the six-membered ring amine (piperidine) should be quite close to that for the acyclic.

Optimize the geometries of aziridine, azetidine, pyrrolidine, and piperidine using the HF/6-31G* model. Starting from these optimized structures, provide guesses at the respective inversion transition states by replacing the tetrahedral nitrogen center with a trigonal center. Obtain transition states using the same Hartree–Fock model and calculate inversion barriers. Calculate vibrational frequencies to verify that you have actually located the appropriate inversion transition states.

Do the calculated inversion barriers follow the order suggested in the preceding figure? If not, which molecule(s) appear to be anomalous? Rationalize your observations by considering other changes in geometry from the amine to the transition state.