Cooperative effect in hydrogen bonding of N-methylacetamide in carbon tetrachloride solution confirmed by NMR and IR spectroscopies

Abstract

Recently we carried out ab initio molecular orbital calculations of the hydrogen bond energies in the dimers and trimers of N-methylacetamide (NMA), and found the existence of a cooperative effect in the hydrogen bonding, by which formation of one hydrogen bond in a hydrogen-bonded chain enhances the strength of another hydrogen bond. In order to confirm the existence of such a cooperative effect, we have determined experimentally the enthalpy changes occurring upon hydrogen bonding of NMA in CCl 4 solution. First, following the method proposed by us, the population fractions of free (non-bonded) NH protons are obtained from the observed amide proton NMR chemical shifts and the IR intensities of the free NH stretching bands. Next, the enthalpy changes are evaluated by analyzing the equilibrium between the free and bonded states of an NH proton. In this analysis, the existence of the CCl 4 solvent is taken into account. The stabilization energy of hydrogen bonds in a trimer, as compared with twice the hydrogen bond energy in a dimer, is 5.4 kJ mol −l, in good agreement with the calculated value (5.9 kJ mol −1). This result provides experimental confirmation of the existence of a cooperative effect in hydrogen bonding.