Syntheses, Single-Crystal Structures, and Structural Chemistry of Hexafluoridouranates(V), MUF6 (M = Li–Cs, Ag, Tl, H3O), and the Dodecafluoridodiuranate(V) Ba[U2F12]·1.36HF
Year: 2025
Type: article
Abstract: High Resolution Image Download MS PowerPoint Slide We present the syntheses of the hexafluoridouranates(V) M UF 6 ( M = Li–Cs, Ag, Tl, H 3 O) and of the dodecafluoridodiuranate(V) Ba[U 2 F 12 ]·1.36HF. With the exception of AgUF 6 and H 3 OUF 6, all compounds were synthesized by reacting the respective metal fluorides with β-UF 5 in anhydrous hydrogen fluoride (aHF). AgUF 6 was obtained as a side product in the oxidation of Ag powder with UF 6 under a CO atmosphere, while H 3 OUF 6 was obtained from the controlled hydrolysis of β-UF 5 with SiO 2 in aHF. For this hydrolysis, silica glass wool proved to be the superior choice of SiO 2 . X-ray diffraction experiments on single crystals of the compounds as well as on polycrystalline samples allowed the unambiguous determination of their crystal structures, clarifying previously published structure models that were based on only powder X-ray diffraction. The structural chemistry of these compounds is discussed. In the case of LiUF 6, NaUF 6, and H 3 OUF 6, molecular UF 6 – anions are observed in the solid state, while one-dimensional infinite strands of ∞ 1 {[UF 4/1 F 4/2 ] − } anions are present in the crystal structures of KUF 6, RbUF 6, TlUF 6, and AgUF 6 . The dodecafluoridodiuranate(V) Ba[U 2 F 12 ]·1.36HF is the second example of a compound containing the peculiar [U 2 F 12 ] 2– anion. Its U atoms show a coordination number of seven in a capped trigonal prismatic coordination sphere, and these prisms share a common edge. In contrast to the Sr homologue, the Ba compound contains HF molecules of crystallization.
Source: Inorganic Chemistry
Institution: Philipps University of Marburg
Language: English
Subfield: Inorganic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,500
Funder: Deutsche Forschungsgemeinschaft
Award: G6120525820
OpenAlex ID: W4413994261