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Issue 10, 2019
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Cations brought together by hydrogen bonds: the protonated pyridine–boronic acid dimer explained

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Abstract

According to the Cambridge Structural Database, protonated pyridine–boronic acid dimers exist in the solid phase, apparently defying repulsive coulombic forces. In order to understand why these cation–cation systems are stable, we carried out M06-2X/6-311++G(3df,2pd) electronic structure calculations and used a set of computational tools (energy partitioning, topology of the electron density and electric field maps). The behavior of the charged dimers was compared with the corresponding neutral systems, and the effect of counterions (Br and BF4) and the solvent (PCM model) on the binding energies has been considered. In the gas-phase, the charged dimers present positive binding energies but are local minima, with a barrier (16–19 kJ mol−1) preventing dissociation. Once the environment is included via solvent effects or counterions, the binding energies become negative; remarkably, the strength of the interaction is very similar in both neutral and charged systems when a polar solvent is considered. Essentially, all methods used evidence that the intermolecular region where the HBs take place is very similar for both neutral and charged dimers. The energy partitioning explains that repulsion and electrostatic terms are compensated by the desolvation and exchange terms in polar solvents, thus giving stability to the charged dimer.

Graphical abstract: Cations brought together by hydrogen bonds: the protonated pyridine–boronic acid dimer explained

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Supplementary files

Article information


Submitted
10 Dec 2018
Accepted
15 Feb 2019
First published
18 Feb 2019

This article is Open Access

Phys. Chem. Chem. Phys., 2019,21, 5796-5802
Article type
Paper

Cations brought together by hydrogen bonds: the protonated pyridine–boronic acid dimer explained

Í. Iribarren, M. M. Montero-Campillo, I. Alkorta, J. Elguero and D. Quiñonero, Phys. Chem. Chem. Phys., 2019, 21, 5796
DOI: 10.1039/C8CP07542E

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