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Int. J. Mol. Sci. 2014, 15(11), 19562-19633; doi:10.3390/ijms151119562

Competing Intramolecular vs. Intermolecular Hydrogen Bonds in Solution

Center for Drug Design and Development, the University of Toledo, Toledo, OH 43606-3390, USA
Received: 12 August 2014 / Revised: 17 September 2014 / Accepted: 13 October 2014 / Published: 28 October 2014
(This article belongs to the Special Issue Chemical Bond and Bonding 2015)
View Full-Text   |   Download PDF [992 KB, uploaded 28 October 2014]   |  

Abstract

A hydrogen bond for a local-minimum-energy structure can be identified according to the definition of the International Union of Pure and Applied Chemistry (IUPAC recommendation 2011) or by finding a special bond critical point on the density map of the structure in the framework of the atoms-in-molecules theory. Nonetheless, a given structural conformation may be simply favored by electrostatic interactions. The present review surveys the in-solution competition of the conformations with intramolecular vs. intermolecular hydrogen bonds for different types of small organic molecules. In their most stable gas-phase structure, an intramolecular hydrogen bond is possible. In a protic solution, the intramolecular hydrogen bond may disrupt in favor of two solute-solvent intermolecular hydrogen bonds. The balance of the increased internal energy and the stabilizing effect of the solute-solvent interactions regulates the new conformer composition in the liquid phase. The review additionally considers the solvent effects on the stability of simple dimeric systems as revealed from molecular dynamics simulations or on the basis of the calculated potential of mean force curves. Finally, studies of the solvent effects on the type of the intermolecular hydrogen bond (neutral or ionic) in acid-base complexes have been surveyed. View Full-Text
Keywords: conformations; tautomerism; aqueous solution; continuum solvent; Monte Carlo; relative free energies; solute dimerization conformations; tautomerism; aqueous solution; continuum solvent; Monte Carlo; relative free energies; solute dimerization
This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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Nagy, P.I. Competing Intramolecular vs. Intermolecular Hydrogen Bonds in Solution. Int. J. Mol. Sci. 2014, 15, 19562-19633.

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