Calcium fluoride is the ultimate source of all fluorochemicals. Current synthetic approaches rely on the use of HF, generated from naturally occurring fluorspar and sulfuric acid. Methods for constructing E–F bonds directly from CaF₂ have long been frustrated by its high lattice energy, low solubility and impaired fluoride ion nucleophilicity. Little fundamental understanding of the reactivity of Ca–F moieties is available to guide methodology development; well-defined molecular species containing Ca–F bonds are extremely rare, and existing examples are strongly aggregated and evidence no nucleophilic fluoride delivery. Here, by contrast, we show that by targeting anionic systems of the type [L_n(X)₂CaF]⁻, monomeric calcium fluoride complexes containing single Ca–F bonds can be synthesized, including via routes involving fluoride abstraction from existing C–F bonds. Comparative structural and spectroscopic studies of mono- and dinuclear systems allow us to define structure–activity relationships for E–F bond formation from molecular calcium fluorides.

氟化钙是所有含氟化合物的最终来源。目前的合成方法依赖于使用由天然萤石和硫酸产生的氟化氢。长期以来，直接从 CaF ₂构建 E-F 键的方法一直因其高晶格能、低溶解度和受损的氟离子亲核性而受挫。对 Ca-F 部分反应性的基本了解无法指导方法开发；含有 Ca-F 键的明确分子种类极为罕见，现有的例子是强烈聚集的，并且证明没有亲核氟化物传递。相比之下，我们在这里表明，通过针对 [L _n (X) ₂ CaF] ⁻类型的阴离子系统，可以合成含有单 Ca–F 键的单体氟化钙络合物，包括通过涉及从现有 C– 中提取氟化物的路线。 F债券。单核和双核系统的比较结构和光谱研究使我们能够定义分子氟化钙形成 E-F 键的结构-活性关系。