The Na+ complexes of 12 substituted aza-crown ethers, some containing amide and others containing ester functional groups as sidearms, were analyzed using dynamic H-1 NMR spectroscopy in CD3CN solution. For the first time the kinetic activation parameters for cation dissociation from the complexes in the case of the 18-C-6 derivatives were measured. These had failed before when using dynamic Na-23 NMR spectroscopy. An interesting exchange mechanism of the cation directly between two ligand molecules was found to predominate for the ligands that contain a tertiary amide substituent, and to a lesser extent an ester group, but not so if the sidearm contains a secondary amide. Such a mechanistic pathway may be important in cation solvation and stabilization within membrane environments. Additional kinetic processes (besides cation exchange) were "frozen" for these complexes at lower temperatures. These have been attributed to macrocycle inversion at nitrogen, which seems to be hindered and thus thermally accessible after formation of the cation-ligand complexes. The two processes, cation exchange and nitrogen inversion, were successfully resolved in some cases, and the kinetic parameters determined independently. Interestingly, for the 15-C-5 derivatives it was found that the two processes have nearly identical activation parameters, indicating that they are probably coupled.