Lewis basicity of relevant monoanions in a non-protogenic organic solvent using a zinc(ii) Schiff-base complex as a reference Lewis acid

Abstract

Anions are ubiquitous species playing a primary role in chemistry, whose reactivity is essentially dominated by their Lewis basicity. However, no Lewis basicity data, in terms of Gibbs energy, are reported in the literature. We report here the first Lewis basicity of relevant monoanions through the determination of binding constants for the formation of stable 1 : 1 adducts, using a Zn^II Schiff-base complex, 1, as a reference Lewis acid. Binding constants for equilibrium reactions were achieved through a nonlinear regression analysis of the binding isotherms from spectrophotometric titration data. The Lewis acidic complex 1 is a proper reference species because it forms stable adducts with both neutral and charged Lewis bases, thus allowing ranking their Lewis basicity. Binding constants indicate generally a strong Lewis basicity for all involved anions, rivalling or exceeding that of the stronger neutral bases, such as primary amines or pyridine. The cyanide anion results to be the strongest Lewis base, while the nitrate is the weaker base within the present anion series. Moreover, even the weaker base anions behave as stronger bases than the most common non-protogenic coordinating solvents.