Affiliation:
1. Anorganische Chemie Fluorchemie Philipps-Universität Marburg Hans-Meerwein-Str. 4 35032 Marburg Germany
2. Department of Chemistry and Materials Science Aalto University 00076 Espoo Finland
Abstract
AbstractThe 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.
Funder
Deutsche Forschungsgemeinschaft
Subject
General Chemistry,Catalysis,Organic Chemistry
Cited by
1 articles.
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