In conclusion, we have synthesized and structurally characterized the first neutral and anionic TACN-supported calcium complexes 2-3, and developed a novel desymmetrization method using iodomethane as a methylating reagent to access the neutral L4X2-supported complex (t-BuTACN-Me)Ca, 4. This complex possesses sufficient Lewis acidity to take up fluoride in benzene or THF solution, generating a series of dinuclear anionic calcium monofluoride complexes 6-8. The doubly bridged Ca2(-F)2 complex 9 could also be synthesized by adding a dilute solution of complex 4 to a concentrated solution of TMAF in THF Scheme 4. Reactivity of Ca-F complex 6 with organic electrophiles. Percentage yield by F NMR using fluorobenzene as internal standard. Crucially, we show enhanced nucleophilic fluoride delivery for 6 over the NON-derived counterparts with respect to Si-and Sbased electrophiles. O-ligation appears to offer higher yields for these electrophiles, on the basis of less competitive side reactions, due to the less nucleophilic nature of the aryloxide X-donors. Furthermore, NMR spectroscopic evidence demonstrates that the fluoride anion from the Ca-F-Ca unit is replaced by the chloride anion from the electrophile. We believe that these findings will inform future work in designing soluble molecular Ca-F complexes, and thus further aid our fundamental understanding of nucleophilicity of the Ca-F bond.