Just Published in Chemical Science

Authors: Ludwig Zapf, Melanie Riethmann, Steffen A. Föhrenbacher, Maik Finze and Udo Radius

Abstract: Steric and electronic effects play a very important role in chemistry, as these effects influence the shape and reactivity of molecules. Herein, an easy-to-perform approach to assess and quantify steric properties of Lewis acids with differently substituted Lewis acidic centers is reported. This model applies the concept of the percent buried volume (%V_Bur) to fluoride adducts of Lewis acids, as many fluoride adducts are crystallographically characterized and are frequently calculated to judge fluoride ion affinities (FIAs). Thus, data such as cartesian coordinates are often easily available. A list of 240 Lewis acids together with topographic steric maps and cartesian coordinates of an oriented molecule suitable for the SambVca 2.1 web application is provided, together with different FIA values taken from the literature. Diagrams of %V_Bur as a scale for steric demand vs. FIA as a scale for Lewis acidity provide valuable information about stereo-electronic properties of Lewis acids and an excellent evaluation of steric and electronic features of the Lewis acid under consideration. Furthermore, a novel LAB-Rep model (Lewis acid/base repulsion model) is introduced, which judges steric repulsion in Lewis acid/base pairs and helps to predict if an arbitrary pair of Lewis acid and Lewis base can form an adduct with respect to their steric properties. The reliability of this model was evaluated in four selected case studies, which demonstrate the versatility of this model. For this purpose, a user-friendly Excel spreadsheet was developed and is provided in the ESI, which works with listed buried volumes of Lewis acids %V_{Bur_LA} and of Lewis bases %V_{Bur_LB}, and no results from experimental crystal structures or quantum chemical calculations are necessary to evaluate steric repulsion in these Lewis acid/base pairs.

Link: https://pubs.rsc.org/en/content/articlelanding/2023/sc/d3sc00037k