Cone Angles Quantify and Predict the Affinity and Reactivity of Anion Complexes between Trifluoroborates and Rigid Macrocycles

Abstract

Steric manipulation is a known concept in molecular recognition but there is currently no linear free energy relationship correlating sterics to the stability of receptor‐anion complexes nor to the reactivity of the bound anion. By analogy to Tolman cone angles in cation coordination chemistry, we explore how to define and correlate cone angles of organo‐trifluoroborates (R–BF3–) to the affinities observed for cyanostar‐anion binding. We extend the analogy to a rare investigation of reactivity and how it changes upon anion binding. The substituent on the anion is used to define the cone angle, θ. A series of 10 anions were studied including versions with ethynyl, ethylene, and ethyl substituents that were selected to tune steric bulk across the sp, sp2 and sp3 hybridized a‐carbons bearing 0, 1 and 2 hydrogen atoms. A linear relationship between affinity and cone angle is observed for anions bearing substituents larger than the –BF3– headgroup. This correlation predicted affinities of two new anions to within ±5%. We explored how complexation affects the reactivity of fluoride exchange. The yield of fluoride transfer from R–BF3– to Lewis acid triphenylborane is correlated with cone angle. We predict that other rigid macrocycles, like commercially available bambusuril, could follow these trends.