Hydrogen bonding. Part 7. A scale of solute hydrogen-bond acidity based on log K values for complexation in tetrachloromethane

TLDR

The study uses the observation that all complexation lines intersect at log K = –1.1 to derive log KAH values, which can be converted to α2H for linear‑regression analysis. A general solute hydrogen‑bond acidity scale comprising 190 log KAH values was established, showing no universal link to proton‑transfer metrics and providing alternative log KAHE values for excluded acid‑base pairs.

Abstract

A scale of solute hydrogen-bond acidity has been constructed using equilibrium constants (as log K values) for complexation of series of acids (i) against a given base in dilute solution in tetrachloromethane, equation (A). Forty-five such equations have been solved to yield LB and DB, log Ki=LB log KAHI+DB(A) values characterising the base, and log KAH values that characterise the acid. In this analysis, use has been made of the novel observation that all the lines in equation (A) intersect at a given point where log K= log KAH=–1.1 with K on the molar scale. Some 190 log KAH values that constitute a reasonably general scale of solute hydrogen-bond acidity have been obtained. It is shown that there is no general connection between log KAH; and any proton-transfer quantities, although certain family dependences are obtained. A number of acid-base combinations are excluded from equation (A), and alternative log KAHE values have been determined for such cases. The general log KAH values may be transformed into α2H values suitable for use in multiple linear-regression analysis through the equation α2H=(log KAH+ 1.1)/4.636.