Stabilization of SF₅⁻ with Glyme-Coordinated Alkali Metal Cations

Abstract

The stabilization of complex fluoroanions derived from weakly acidic parent fluorides is a significant and ongoing challenge. The [SF₅]⁻ anion is recognized as one such case, and only a limited number of [SF₅]⁻ salts are known to be stable at room temperature. In the present study, glyme-coordinated alkali metal cations (K⁺, Rb⁺, and Cs⁺) are employed to stabilize [SF₅]⁻, which provides a simple synthetic route to a [SF₅]⁻ salt. The reactivities of KF and RbF with SF₄ are significantly enhanced by complexation with G4, based on Raman spectroscopic analyses. A new room-temperature stable salt, [Cs(G4)₂][SF₅] (G4 = tetraglyme), was synthesized by stoichiometric reaction of CsF, G4, and SF₄. The vibrational frequencies of [SF₅]⁻ were assigned based on quantum chemical calculations, and the shift of the G4 breathing mode accompanying coordination to metal cations was confirmed by Raman spectroscopy. Single-crystal X-ray diffraction revealed that Cs⁺ is completely isolated from [SF₅]⁻ by two G4 ligands and [SF₅]⁻ is disordered along the crystallographic two-fold axis. Hirshfeld surface analysis reveals that the H···H interaction between two neighboring [Cs(G4)₂]⁺ moieties is more dominant on the Hirshfeld surface than the interaction between the H atom in glyme molecules and the F atom in [SF₅]⁻, providing a CsCl-type structural model where the large and spherical [Cs(G4)₂]⁺ cations contact each other and the [SF₅]⁻ anions occupy interstitial spaces in the crystal lattice. The [SF₅]⁻ anion, combined with [Cs(G4)₂]⁺, exhibits a very limited deoxofluorinating ability toward hydroxyl groups in both neat conditions and THF solutions.