4.6 Article

Aldiminium Cations as Countercations to Discrete Main Group Fluoroanions

Journal

MOLECULES
Volume 28, Issue 17, Pages -

Publisher

MDPI
DOI: 10.3390/molecules28176270

Keywords

aldiminium-based salts; CAAC-precursors; fluorination; pentafluorosilicate; pentafluorogermanate; synthesis

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The reactions between the CAAC-based trifluoride reagent and group 14 tetrafluorides and group 15 pentafluorides resulted in the isolation of salts containing discrete 5- or 6-coordinated fluoroanions. The synthesized compounds were characterized by X-ray single-crystal structure analysis, NMR, and Raman spectroscopy. Notably, [MeCAACH][GeF5] is a rare structurally characterized compound with a discrete [GeF5]- anion.
The reactions of group 14 tetrafluorides (SiF4, GeF4, and SnF4) and group 15 pentafluorides (PF5, AsF5, and SbF5) with the CAAC-based trifluoride reagent [MeCAACH][F(HF)2] led to the isolation of salts containing discrete 5- or 6-coordinated fluoroanions. The syntheses of [MeCAACH][SiF5], [MeCAACH][GeF5], [MeCAACH][(THF)SnF5], and the structurally related [MeCAACH][(dioxane)SnF5], [MeCAACH][PF6], [MeCAACH][AsF6], and [MeCAACH][SbF6] 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 [MeCAACH][GeF5] is a rare example of a structurally characterized compound with discrete [GeF5]- anion, while [MeCAACH][(THF)SnF5] and [MeCAACH][(dioxane)SnF5] represent the first compounds with discrete octahedrally coordinated tin fluoride anions with incorporated solvent molecules. Finally, the aldiminium-based cation [MeCAACH]+ proved to be suitable for the stabilization of rare discrete main group fluoride anions.

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