Localization and moving of a proton inside hydrogen-bonded complexes in aprotic solvents

The results of the study of a number of molecular and ionic H-bonded complexes in freon solutions by ¹H NMR at 100–150 K are reported. It is shown that under these conditions the signals of OH(NH) protons belonging to various complexes, self-associates and free molecules are observed separately. The spin-spin coupling of the signals is frequently discernible. The fine structure makes it possible to distinguish between complexes with fast proton migration between two wells on the potential surface and those with the proton localized in one well (in particular, the central one). Several complexes with slow (in the NMR scale) proton migration have also been found.The results of the study of the non-catalytic proton exchange kinetics between various molecules containing OH and NH groups in dilute solutions in aprotic solvents are considered. The exchange between the RCOOH and ROH molecules goes on via the intermediate formation of a cyclic ionic pair with two equivalent H-bonds even in non-polar solvents such as cyclohexane. For exchange between two RCOOH or ROH molecules a synchronous transfer of two protons in a cyclic molecular complex is likely.