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

Martin Möbs; Tim Graubner; Antti J. Karttunen; Florian Kraus

doi:10.1002/chem.202301876

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

Martin Möbs
, Tim Graubner
, Antti J. Karttunen
, Florian Kraus^*

^*Tämän työn vastaava kirjoittaja

University of Marburg

Tutkimustuotos: Lehtiartikkeli › Article › Scientific › vertaisarvioitu

5 Sitaatiot (Scopus)

106 Lataukset (Pure)

Abstrakti

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.

Alkuperäiskieli	Englanti
Artikkeli	e202301876
Julkaisu	Chemistry: A European Journal
Vuosikerta	29
Numero	49
Varhainen verkossa julkaisun päivämäärä	31 heinäk. 2023
DOI - pysyväislinkit	https://doi.org/10.1002/chem.202301876
Tila	Julkaistu - 1 syysk. 2023
OKM-julkaisutyyppi	A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä

Rahoitus

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.

Pääsy asiakirjaan

10.1002/chem.202301876Lisenssi: CC BY

CHEM_Moebs_et_al_m3‐F-BrF53-_An_Unprecedented_Molecular_2023_Chemistry_A_European_JournalFinal published version, 2,77 MBLisenssi: CC BY

Muut tiedostot ja linkit

CSD 2261797: Experimental Crystal Structure Determination
Möbs, M. (Creator), Graubner, T. (Creator), Karttunen, A. J. (Creator) & Kraus, F. (Creator), FIZ Karlsruhe - Leibniz Institute for Information Infrastructure, 8 toukok. 2023
DOI - pysyväislinkki: 10.25505/fiz.icsd.cc2fxl65, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.25505/fiz.icsd.cc2fxl65&sid=DataCite
Tietoaineisto: Dataset

Siteeraa tätä

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

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.",

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

author = "Martin M{\"o}bs and Tim Graubner and Karttunen, \{Antti J.\} and Florian Kraus",

note = "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: {\textcopyright} 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.",

year = "2023",

month = sep,

day = "1",

doi = "10.1002/chem.202301876",

language = "English",

volume = "29",

journal = "Chemistry: A European Journal",

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T1 - [(μ3-F)(BrF5)3]− – An Unprecedented Molecular Fluoridobromate(V) Anion in Cs[Br3F16]

AU - Möbs, Martin

AU - Graubner, Tim

AU - Karttunen, Antti J.

AU - Kraus, Florian

N1 - 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.

PY - 2023/9/1

Y1 - 2023/9/1

N2 - 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.

AB - 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.

KW - bromine pentafluoride

KW - crystal structure

KW - fluorine

KW - interhalogen compounds

KW - quantum-chemical calculation

UR - https://www.scopus.com/pages/publications/85166241579

UR - https://doi.org/10.1002/chem.202303053

U2 - 10.1002/chem.202301876

DO - 10.1002/chem.202301876

M3 - Article

AN - SCOPUS:85166241579

SN - 0947-6539

VL - 29

JO - Chemistry: A European Journal

JF - Chemistry: A European Journal

IS - 49

M1 - e202301876

ER -