Discrete Mono-, Di-, and Trinuclear Anions [MoOF], [MoOF], [MoOF], [MoOF], [MoOF], and the Infinite Chain Anion [MoOF] Obtained from Reactions of MoOF: Synthesis and Analysis of the Structure-Chemical Relations of the Compounds.

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.