Wassermann Tobias B, Stene Riane E, Scheibe Benjamin, Karttunen Antti J, Kraus Florian
Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Str. 4, Marburg, Hessen 35032, Germany.
Department of Chemistry and Materials Science, Aalto University, Kemistintie 1, Aalto 00076, Finland.
Inorg Chem. 2023 Aug 21;62(33):13435-13452. doi: 10.1021/acs.inorgchem.3c01792. Epub 2023 Aug 9.
The herein-reported oxyfluoridometallate salts were synthesized and structurally characterized during the studies of the Lewis acidity of OF ( = Mo, W) with various fluoride ion donors (RbF, CsF, TlF, AgF, SrF, BaF, PbF) in different solvents (aqHF 48%, aHF, BrF, ClF). Phase-pure MoOF was either synthesized by hydrolysis of MoF with SiO in anhydrous HF (aHF) or by reactions of BrF with MoO or MoO, 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. MoOF reacted with PbF in aHF forming Pb[MoOF], while under comparable conditions, WOF formed Pb[WOF]F, containing the [WOF] anion. Salts containing such [MoOF] anions were also directly obtained from reactions of BrF, MoO, and F ( = Sr, Ba), while with AgF, the compound Ag[MoOF] was observed. ClF reacted with MoO to form [ClOF][MoOF]. Carrying out similar reactions in aqueous HF (aqHF) in autoclaves under hydrofluorothermal conditions leads to O-richer compounds with the composition [MoOF] ( = Sr, Ba). With RbF or Tl(CO), the compounds [MoOF] ( = Rb, Tl) were obtained. With CsF reduction to Mo(V) occurred as Cs[MoOF] was formed. We report on similarities and differences within the respective anions and within the crystal structures of these compounds.
本文报道的氧氟金属酸盐是在研究OF（=Mo，W）与各种氟离子供体（RbF、CsF、TlF、AgF、SrF、BaF、PbF）在不同溶剂（48%的氢氟酸水溶液、无水氢氟酸、BrF、ClF）中的路易斯酸度过程中合成并进行结构表征的。纯相的MoOF可通过MoF与SiO在无水氢氟酸（aHF）中水解合成，也可分别通过BrF与MoO或MoO反应合成。该化合物通过红外光谱和拉曼光谱、固态量子化学计算以及粉末和单晶X射线衍射进行表征。MoOF在aHF中与PbF反应形成Pb[MoOF]，而在类似条件下，WOF形成含[WOF]阴离子的Pb[WOF]F。含有此类[MoOF]阴离子的盐也可直接通过BrF、MoO和F（=Sr，Ba）反应获得，而与AgF反应时，观察到化合物Ag[MoOF]。ClF与MoO反应形成[ClOF][MoOF]。在高压釜中于氢氟酸水溶液（aqHF）中在水热氟条件下进行类似反应会生成组成更富氧的化合物[MoOF]（=Sr，Ba）。与RbF或Tl(CO)反应可得到化合物[MoOF]（=Rb，Tl）。与CsF反应时会发生还原生成Mo(V)，因为会形成Cs[MoOF]。我们报道了这些化合物各自阴离子以及晶体结构中的异同。
