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.

The herein-reported oxyfluoridometallate salts were synthesized and structurally characterized during the studies of the Lewis acidity of M OF 4 ( M = Mo, W) with various fluoride ion donors (RbF, CsF, TlF, AgF, SrF 2 , BaF 2 , PbF 2 ) in different solvents (aqHF 48%, aHF, BrF 3 , ClF 3 ). Phase-pure MoOF 4 was either synthesized by hydrolysis of MoF 6 with SiO 2 in anhydrous HF (aHF) or by reactions of BrF 3 with MoO 2 or MoO 3 , 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 4 reacted with PbF 2 in aHF forming Pb[MoOF 5 ] 2 , while under comparable conditions, WOF 4 formed Pb 3 [WOF 5 ] 4 F 2 , containing the [WOF 5 ] - anion. Salts containing such [MoOF 5 ] - anions were also directly obtained from reactions of BrF 3 , MoO 3 , and A F 2 ( A = Sr, Ba), while with AgF, the compound Ag[Mo 2 O 2 F 9 ] was observed. ClF 3 reacted with MoO 3 to form [ClOF 2 ][Mo 3 O 3 F 13 ]. Carrying out similar reactions in aqueous HF (aqHF) in autoclaves under hydrofluorothermal conditions leads to O-richer compounds with the composition A [MoO 2 F 4 ] ( A = Sr, Ba). With RbF or Tl 2 (CO 3 ), the compounds A [MoO 2 F 3 ] ( A = Rb, Tl) were obtained. With CsF reduction to Mo(V) occurred as Cs 2 [Mo V OF 5 ] was formed. We report on similarities and differences within the respective anions and within the crystal structures of these compounds.