On pK<inf>a</inf> matching as a requirement to form a low-barrier hydrogen bond. A theoretical study in gas phase

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Abstract

Theoretical calculations in the gas phase on a series of intermolecular complexes formed between 1-methylimidazole (1-MeIm) and four carboxylic acids R-COOH, where R = CF3, CHCl2, C(CH3)Cl2, and CH2Cl, have been carried out. Results from NMR and FTIR spectroscopy, in previous experimental studies, have been used by Frey and co-workers, trying to characterize the hydrogen bond between those carboxylic acids and 1-methylimidazole in aprotic organic solvents. Our energetic results for the proton transfer through the hydrogen bond indicate that only one of the carboxylic acids is able to form a low-barrier hydrogen bond (LBHB) with 1-MeIm in gas phase. However, there is not equalization between the pKas of R-COOH and 1-MeImH+ (the conjugate acid of 1-MeIm). We suggest that, for short hydrogen bonds, a requirement for forming a LBHB is energy degeneration (or nearly degeneration) of the two minima in a double-well hydrogen bond. This energy degeneration in the double well is determined by a thermodynamic cycle where the pKa difference of the conjugate acids of the interacting groups is one of the factors taken into account. We have also shown that a delocalized LBHB is not necessarily stronger than a localized hydrogen bond. Along with the thermodynamic results, an analysis of the electronic wave function at several stationary points of the different complexes is presented.
Original languageEnglish
Pages (from-to)3880-3886
JournalJournal of Physical Chemistry A
Volume101
Issue number21
Publication statusPublished - 22 May 1997

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