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.