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Title: Stabilization of SF₅⁻ with Glyme-Coordinated Alkali Metal Cations
Authors: Matsumoto, Kazuhiko  kyouindb  KAKEN_id  orcid (unconfirmed)
Haruki, Yuki
Sawada, Shunsuke
Yamada, Shigeyuki
Konno, Tsutomu
Hagiwara, Rika  kyouindb  KAKEN_id  orcid (unconfirmed)
Author's alias: 松本, 一彦
澤田, 峻佑
萩原, 理加
Keywords: Physical and Theoretical Chemistry
Inorganic Chemistry
Issue Date: 3-Dec-2018
Publisher: American Chemical Society (ACS)
Journal title: Inorganic chemistry
Volume: 57
Start page: 14882
End page: 14889
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.
Rights: This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see
This is not the published version. Please cite only the published version. この論文は出版社版でありません。引用の際には出版社版をご確認ご利用ください。
DOI(Published Version): 10.1021/acs.inorgchem.8b02655
PubMed ID: 30444364
Appears in Collections:Journal Articles

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