Multidimensional Lewis Acidity: A Consistent Data Set of Chloride, Hydride, Methide, Water and Ammonia Affinities for 183 p-Block Element Lewis Acids.

Abstract

The computed fluoride ion affinity (FIA) is a widely applied descriptor to gauge Lewis acidity. Like every other single‐parameter Lewis acidity scale, the FIA metric suffers from the one‐dimensionality, that prohibits addressing Lewis acidity by the multidimensionality it inherently requires (i. e., reference Lewis base dependency). However, a systematic screening of computed affinities other than the FIA is much less developed. Herein, we extended our CCSD(T)/CBS benchmark of different density functionals and the DLPNO‐CCSD(T) method for chloride (CIA), methide (MIA), hydride (HIA), water (WA), and ammonia (AA) affinities. The best performing methods are subsequently applied to yield nearly 800 affinities for 183 p‐block element compounds of group 13–16 with an estimated accuracy of <10 kJ mol−1. The study‘s output serves as a consistent library for qualitative analyses and a training set for future statistical approaches. A first holistic correlation analysis underscores the need for a multidimensional description of Lewis acidity.