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Title: Stabilization of SF₅⁻ with Glyme-Coordinated Alkali Metal Cations
Authors: Matsumoto, Kazuhiko  kyouindb  KAKEN_id  orcid https://orcid.org/0000-0002-0770-9210 (unconfirmed)
Haruki, Yuki
Sawada, Shunsuke
Yamada, Shigeyuki
Konno, Tsutomu
Hagiwara, Rika  kyouindb  KAKEN_id  orcid https://orcid.org/0000-0002-7234-3980 (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 https://doi.org/10.1021/acs.inorgchem.8b02655.
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。
URI: http://hdl.handle.net/2433/245207
DOI(Published Version): 10.1021/acs.inorgchem.8b02655
PubMed ID: 30444364
Appears in Collections:Journal Articles

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