Nucleophilic Fluoride Anion Delivery from Triazacyclononane‐Supported Molecular Ca–F Complexes

The major source of fluoride, namely calcium difluoride (CaF₂), is derived from the mineral fluorspar. Recent advances in the activation of CaF₂ via mechanochemical methods have inspired investigation of the fundamental properties of Ca-F bonds in molecular complexes. However, the paucity of well-defined molecular Ca-F-containing complexes undermines systematic understanding of the factors governing nucleophilic fluoride delivery. Here we report the use of a multidentate bis(phenoxide) ligand based on a 1,4,7-triazacyclononane (TACN) scaffold for the formation of well-defined Ca-F complexes and demonstrate their capabilities in fluoride delivery. Key to this synthesis is a desymmetrization step carried out on the TACN ligand within the Ca coordination sphere. A series of stable anionic dinuclear calcium fluoride complexes has then been accessed and characterized by NMR spectroscopy (critically by ¹⁹F NMR) and X-ray crystallography. Nucleophilic fluoride delivery can be used to generate C-F, Si-F and S-F bonds, with a notable advance over amide-derived ligand scaffolds being the reduced extent of side reactions derived from competing attack on the electrophile by the less nucleophilic O-donor anionic ligand set.