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PbF[Br 2 F 7 ], a Fluoridobromate(III) of a p‐Block Metal
Author(s) -
Bandemehr Jascha,
Sachs Malte,
Ivlev Sergei I.,
Karttunen Antti J.,
Kraus Florian
Publication year - 2020
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201901041
Subject(s) - chemistry , raman spectroscopy , crystallography , block (permutation group theory) , powder diffraction , crystal structure , single crystal , metal , infrared spectroscopy , diffraction , analytical chemistry (journal) , organic chemistry , physics , geometry , mathematics , optics
The compound PbF[Br 2 F 7 ] represents the first fluoridobromate(III) of a p‐block element. It was synthesized in form of needle‐shaped crystals among its colorless powder from the direct reaction of PbF 2 with BrF 3 . Powder X‐ray diffraction, IR and Raman spectroscopy show that it was obtained in almost pure form with Pb 3 F 8 and Pb 2 F 6 as by‐products. The single crystal structure was determined by X‐ray diffraction. PbF[Br 2 F 7 ] crystallizes in space group P 2 1 / c (No. 14) with a = 4.3698(3), b = 13.3767(7), c = 12.0836(8) Å, β = 97.509(5)°, V = 700.27(8) Å 3 , Z = 4 at T = 100 K. PbF[Br 2 F 7 ] decomposes above 50 °C due to loss of BrF 3 and pure PbF 2 remains. Quantum chemical calculations were performed on the crystal structure of the compound to assign the bands of the vibrational spectra and to obtain electron density difference maps that visualize the electron density around the Pb atoms. CHARDI calculations support the assignment of the oxidation states +II, +III, and –I to the Pb, Br, and F atoms, respectively.