Discrete Mono-, Di-, and Trinuclear Anions [MoOF5]−, [MoVOF5]2-, [MoO2F4]2-, [Mo2O2F9]−, [Mo3O3F13]−, and the Infinite Chain Anion [MoO2F3]− Obtained from Reactions of MoOF4: Synthesis and Analysis of the Structure-Chemical Relations of the Compounds
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A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä
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2023-08-21
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en
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Inorganic Chemistry, Volume 62, issue 33, pp. 13435-13452
Abstract
The herein-reported oxyfluoridometallate salts were synthesized and structurally characterized during the studies of the Lewis acidity of MOF4 (M = Mo, W) with various fluoride ion donors (RbF, CsF, TlF, AgF, SrF2, BaF2, PbF2) in different solvents (aqHF 48%, aHF, BrF3, ClF3). Phase-pure MoOF4 was either synthesized by hydrolysis of MoF6 with SiO2 in anhydrous HF (aHF) or by reactions of BrF3 with MoO2 or MoO3, respectively. The compound was characterized by infrared and Raman spectroscopy, solid-state quantum-chemical calculations, as well as powder and single-crystal X-ray diffraction. MoOF4 reacted with PbF2 in aHF forming Pb[MoOF5]2, while under comparable conditions, WOF4 formed Pb3[WOF5]4F2, containing the [WOF5]− anion. Salts containing such [MoOF5]− anions were also directly obtained from reactions of BrF3, MoO3, and AF2 (A = Sr, Ba), while with AgF, the compound Ag[Mo2O2F9] was observed. ClF3 reacted with MoO3 to form [ClOF2][Mo3O3F13]. Carrying out similar reactions in aqueous HF (aqHF) in autoclaves under hydrofluorothermal conditions leads to O-richer compounds with the composition A[MoO2F4] (A = Sr, Ba). With RbF or Tl2(CO3), the compounds A[MoO2F3] (A = Rb, Tl) were obtained. With CsF reduction to Mo(V) occurred as Cs2[MoVOF5] was formed. We report on similarities and differences within the respective anions and within the crystal structures of these compounds.Description
Funding Information: We would like to thank Solvay for the kind donations of F, Dr. Tambornino, Dr. Ivlev, and Dr. Conrad for helpful discussions, and the Deutsche Forschungsgemeinschaft for funding (KR3595/15-1). 2 Publisher Copyright: © 2023 American Chemical Society
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Wassermann, T B, Stene, R E, Scheibe, B, Karttunen, A J & Kraus, F 2023, ' Discrete Mono-, Di-, and Trinuclear Anions [MoOF 5 ] −, [Mo V OF 5 ] 2-, [MoO 2 F 4 ] 2-, [Mo 2 O 2 F 9 ] −, [Mo 3 O 3 F 13 ] −, and the Infinite Chain Anion [MoO 2 F 3 ] − Obtained from Reactions of MoOF 4 : Synthesis and Analysis of the Structure-Chemical Relations of the Compounds ', Inorganic Chemistry, vol. 62, no. 33, pp. 13435-13452 . https://doi.org/10.1021/acs.inorgchem.3c01792