Correlations of NHN hydrogen bond energy with geometry and 1H NMR chemical shift difference of NH protons for aniline complexes

E. Yu. Tupikina , M. Sigalov, Ilya G. Shenderovich, V. V. Mulloyarova, G. S. Denisov, P. M. Tolstoy

Research output

1 Citation (Scopus)

Abstract

In this computational work, we propose to use the NMR chemical shift difference of NH 2 protons for 1:1 complexes formed by aniline and nitrogen-containing proton acceptors for the estimation of the hydrogen bond energy and geometry (N⋯H and N⋯N distances). The proposed correlations could be applied to other aromatic amines as well, in a gas phase, a solution, or a solid state, for both inter- and intramolecular hydrogen bonds. We considered a set of 21 complexes with the NHN hydrogen bond without proton transfer, including hydrogen bonds from weak to medium strong ones (2-21 kcal/mol), with neutral or anionic bases and with sp 3 and sp 2 hybridized nitrogen proton acceptors. For each complex apart from direct hydrogen bond energy calculation, we have tested several other ways to estimate the energy: (a) using a correlation between NH stretching band intensity and hydrogen bond energy and (b) using correlations between electron density properties at (3, -1) bond critical point (quantum theory of atoms in molecules analysis) and hydrogen bond energy. Besides for the studied type of complexes, we obtained refined linear correlations linking the local electron kinetic (G) and potential (V) energy densities with the hydrogen bond energy.

Original languageEnglish
Article number114305
Pages (from-to)1-10
Number of pages10
JournalJournal of Chemical Physics
Volume150
Issue number11
DOIs
Publication statusPublished - 21 Mar 2019

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Chemical shift
aniline
chemical equilibrium
Protons
Hydrogen bonds
Nuclear magnetic resonance
hydrogen bonds
nuclear magnetic resonance
protons
Geometry
geometry
energy
Nitrogen
nitrogen
Proton transfer
Quantum theory
quantum theory
Stretching
Amines
Carrier concentration

Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

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title = "Correlations of NHN hydrogen bond energy with geometry and 1H NMR chemical shift difference of NH protons for aniline complexes",
abstract = "In this computational work, we propose to use the NMR chemical shift difference of NH 2 protons for 1:1 complexes formed by aniline and nitrogen-containing proton acceptors for the estimation of the hydrogen bond energy and geometry (N⋯H and N⋯N distances). The proposed correlations could be applied to other aromatic amines as well, in a gas phase, a solution, or a solid state, for both inter- and intramolecular hydrogen bonds. We considered a set of 21 complexes with the NHN hydrogen bond without proton transfer, including hydrogen bonds from weak to medium strong ones (2-21 kcal/mol), with neutral or anionic bases and with sp 3 and sp 2 hybridized nitrogen proton acceptors. For each complex apart from direct hydrogen bond energy calculation, we have tested several other ways to estimate the energy: (a) using a correlation between NH stretching band intensity and hydrogen bond energy and (b) using correlations between electron density properties at (3, -1) bond critical point (quantum theory of atoms in molecules analysis) and hydrogen bond energy. Besides for the studied type of complexes, we obtained refined linear correlations linking the local electron kinetic (G) and potential (V) energy densities with the hydrogen bond energy.",
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T1 - Correlations of NHN hydrogen bond energy with geometry and 1H NMR chemical shift difference of NH protons for aniline complexes

AU - Tupikina , E. Yu.

AU - Sigalov, M.

AU - Shenderovich, Ilya G.

AU - Mulloyarova, V. V.

AU - Denisov, G. S.

AU - Tolstoy, P. M.

PY - 2019/3/21

Y1 - 2019/3/21

N2 - In this computational work, we propose to use the NMR chemical shift difference of NH 2 protons for 1:1 complexes formed by aniline and nitrogen-containing proton acceptors for the estimation of the hydrogen bond energy and geometry (N⋯H and N⋯N distances). The proposed correlations could be applied to other aromatic amines as well, in a gas phase, a solution, or a solid state, for both inter- and intramolecular hydrogen bonds. We considered a set of 21 complexes with the NHN hydrogen bond without proton transfer, including hydrogen bonds from weak to medium strong ones (2-21 kcal/mol), with neutral or anionic bases and with sp 3 and sp 2 hybridized nitrogen proton acceptors. For each complex apart from direct hydrogen bond energy calculation, we have tested several other ways to estimate the energy: (a) using a correlation between NH stretching band intensity and hydrogen bond energy and (b) using correlations between electron density properties at (3, -1) bond critical point (quantum theory of atoms in molecules analysis) and hydrogen bond energy. Besides for the studied type of complexes, we obtained refined linear correlations linking the local electron kinetic (G) and potential (V) energy densities with the hydrogen bond energy.

AB - In this computational work, we propose to use the NMR chemical shift difference of NH 2 protons for 1:1 complexes formed by aniline and nitrogen-containing proton acceptors for the estimation of the hydrogen bond energy and geometry (N⋯H and N⋯N distances). The proposed correlations could be applied to other aromatic amines as well, in a gas phase, a solution, or a solid state, for both inter- and intramolecular hydrogen bonds. We considered a set of 21 complexes with the NHN hydrogen bond without proton transfer, including hydrogen bonds from weak to medium strong ones (2-21 kcal/mol), with neutral or anionic bases and with sp 3 and sp 2 hybridized nitrogen proton acceptors. For each complex apart from direct hydrogen bond energy calculation, we have tested several other ways to estimate the energy: (a) using a correlation between NH stretching band intensity and hydrogen bond energy and (b) using correlations between electron density properties at (3, -1) bond critical point (quantum theory of atoms in molecules analysis) and hydrogen bond energy. Besides for the studied type of complexes, we obtained refined linear correlations linking the local electron kinetic (G) and potential (V) energy densities with the hydrogen bond energy.

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