Well-defined Ca-F complexes remain scarce in the chemical literature, with the few existing reports ranging from inorganic clusters to main group complexes. Although structurally sophisticated, such cluster complexes typically display bridging Ca-F bond motifs as part of extended cages. In contrast, the -diketiminate systems independently reported by Roesky and by Barrett and Hill offered solubility in hydrocarbon solvents, and represented the first well-defined dimeric Ca-F complexes (Figure ). However, neither system exemplifies any nucleophilic fluoride anion delivery. Recently, our group reported the synthesis and reactivity of Ca-F-containing complexes stabilized by the 4,5-bis(2,6-diisopropylanilido)-2,7-di-tertbutyl-9,9-dimethylxanthene (NON) ligand. The reported complexes are unique in being able to deliver fluoride to electrophilic substrates, to an extent which increases as the Ca-F moiety becomes less sterically congested.