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A Study of the Abraham Effective Solute Hydrogen Bond Basicity Parameter Using Computationally Derived Molecular Properties

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Abstract

Abraham’s measure of the solute hydrogen bond basicity, \(\beta_{2}^{{\text{H}}}\), is analyzed in terms of molecular properties derived from computational chemistry. It is found that the solute basicity is largely determined by the partial charges on negative centers on the solute molecule. For \(\beta_{2}^{{\text{H}}}\) < 0.5 the basicity is determined by the partial charge on the most negative atom of the solute molecule but for multifunctional solutes with higher \(\beta_{2}^{{\text{H}}}\) values there are contributions from the basicity of other basic centers. The \(\beta_{2}^{{\text{H}}}\) values of amines are not reproduced by the equation defined by correlation of the other solutes considered.

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Notes

  1. This is, of course, well known and was the basis of Kamlet and Taft’s scale of hydrogen bond acidities [6 and references therein].

  2. The quadrupolar amplitude is calculated as \(A = \sqrt {\sum {q_{ij} q_{ij} } } \, \, i = x,y,z \, {\text{and}} \, j = x,y,z\) where the qij are the components of the traceless quadrupole.

    Complex charge distributions, such as those of polyatomic molecules, are commonly represented by a series of superimposed point objects. The first is a point charge (the net charge), which is a scalar quantity, the second is the dipole, which is a vector and the third is the quadrupole, which is a tensor. Just as the dipole has no net charge, the quadrupole has no net moment. The dipole moment and quadrupolar amplitude are used here simply as quantitative measures of the scale of charge centers imbedded in the bulk solvent, the “intensity” of embedded charges. The simplest way to see the necessity for both the dipolar and quadrupolar contributions is to consider CO2, which, despite having partial charges on the O and C atoms has a zero dipole moment, but a non-zero quadrupolar amplitude.

  3. For clarity, the convention is adopted that \(\beta_{2}^{{\text{H}}}\) refers to the experimentally determined basicity parameter, \(\beta_{2}^{{\text{H*}}}\) represents the basicity parameter calculated using Eq. 4 and the coefficients listed in Table 1. Where hydrogen bonding to more than one site on the solute molecule is considered, \(\beta_{2i}^{{\text{H*}}}\) represents the calculated basicity parameter for site i on the solute molecule and \(\sum {\beta_{2}^{{\text{*H}}} }\) is the sum of the calculated \(\beta_{2i}^{{\text{H*}}}\) for the various sites on the solute molecule.

  4. The values for the methyl and ethyl acids and esters are slightly lower.

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  1. School of Chemistry, University College Dublin, Belfield, Dublin 4, Ireland

    W. Earle Waghorne

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Waghorne, W.E. A Study of the Abraham Effective Solute Hydrogen Bond Basicity Parameter Using Computationally Derived Molecular Properties. J Solution Chem 51, 1133–1147 (2022). https://doi.org/10.1007/s10953-022-01168-w

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