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Re-interpretation of the solvent dielectric constant in coordination chemical terms

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Abstract

It is found for common aprotic solvents that the logarithm of the dielectric constants can be represented by a linear combination of the acceptor numbers (AN) and the donor numbers (DN) (or equivalent parameters),

$$log \in = c_1 ({\rm A}{\rm N}){\text{ }} + {\text{ }}c_2 (DN){\text{ }} + {\text{ }}c_3 $$

With this equation, concepts of specific and non-specific solvation are brought under the umbrella of one treatment. The equation does not hold for the highly structured solvents. For these, the dielectric constants predicted on the basis of the acceptor and donor numbers are orders of magnitude larger than the experimental values, revealing how poorly the associates are dissociated by the macroscopically attainable electric fields.

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Schmid, R. Re-interpretation of the solvent dielectric constant in coordination chemical terms. J Solution Chem 12, 135–152 (1983). https://doi.org/10.1007/BF00645354

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Key words

  • Dielectric constant
  • empirical solvent parameters
  • associated solvents
  • solvent-reactivity correlations