[(μ3-F)(BrF5)3]− – An Unprecedented Molecular Fluoridobromate(V) Anion in Cs[Br3F16]

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A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä

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2023-09-01

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en

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Chemistry: A European Journal, Volume 29, issue 49

Abstract

The reaction of Cs[BrF6] with BrF5 gave the compound Cs[Br3F16] with the unprecedented propeller-shaped, C3-symmetric [(μ3-F)(BrF5)3]− anion. All other currently known fluoridobromates(V) contain only octahedral [BrF6]− anions, which, unlike the related [IF6]− anions, never exhibited stereochemical activity of the lone pair on the Br atoms. Despite the same coordination number of six for the Br atom in the [BrF6]− and [(μ3-F)(BrF5)3]− anions, the longer μ3-F−Br bonds provide additional space, allowing the lone pairs on the Br atoms to become stereochemically active. Cs[Br3F16] was characterized by single-crystal X-ray diffraction, Raman spectroscopy, and quantum-chemical calculations for both the solid-state compound and the isolated anion at 0 K. Intrinsic bond orbital calculations show that the μ3-F−Br bond is essentially ionic in nature and also underpin the stereochemical activity of the lone pairs of the Br(V) atoms.

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Funding Information: M. M. thanks Dr. Matthias Conrad for helpful discussions. We thank Dr. Sergei I. Ivlev for his excellent X‐ray facilities. We thank Solvay for the kind donations of fluorine. We thank the Deutsche Forschungsgemeinschaft, CRC 1487, for funding. A. J. K. thanks CSC, the Finnish IT Center for Science for computational resources. Open Access funding enabled and organized by Projekt DEAL. Publisher Copyright: © 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.

Keywords

bromine pentafluoride, crystal structure, fluorine, interhalogen compounds, quantum-chemical calculation

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Citation

Möbs, M, Graubner, T, Karttunen, A J & Kraus, F 2023, ' [(μ 3 -F)(BrF 5 ) 3 ] − – An Unprecedented Molecular Fluoridobromate(V) Anion in Cs[Br 3 F 16 ] ', Chemistry: A European Journal, vol. 29, no. 49, e202301876 . https://doi.org/10.1002/chem.202301876