Abstract
The reactions of group 14 tetrafluorides (SiF(4), GeF(4), and SnF(4)) and group 15 pentafluorides (PF(5), AsF(5), and SbF(5)) with the CAAC-based trifluoride reagent [(Me)CAACH][F(HF)(2)] led to the isolation of salts containing discrete 5- or 6-coordinated fluoroanions. The syntheses of [(Me)CAACH][SiF(5)], [(Me)CAACH][GeF(5)], [(Me)CAACH][(THF)SnF(5)], and the structurally related [(Me)CAACH][(dioxane)SnF(5)], [(Me)CAACH][PF(6)], [(Me)CAACH][AsF(6)], and [(Me)CAACH][SbF(6)] are effective, selective and in high yield. All compounds were characterized by X-ray single-crystal structure analysis, NMR and Raman spectroscopy. It is worth noting that the synthesized [(Me)CAACH][GeF(5)] is a rare example of a structurally characterized compound with discrete [GeF(5)](-) anion, while [(Me)CAACH][(THF)SnF(5)] and [(Me)CAACH][(dioxane)SnF(5)] represent the first compounds with discrete octahedrally coordinated tin fluoride anions with incorporated solvent molecules. Finally, the aldiminium-based cation [(Me)CAACH](+) proved to be suitable for the stabilization of rare discrete main group fluoride anions.