Dimethylhydroxyoxosulfonium(VI) Hexafluoridometallates, [(CH3)2SO(OX)]+[MF6]–(X = H,D; M = As,Sb)

Dimethylsulfone reacts in the binary superacidic systems XF/MF₅ (X = H, D; M = As, Sb) under the formation of the corresponding salts of the type (CH₃)₂SO(OX)]⁺MF₆]^–. The salts are characterized by low temperature vibrational spectroscopy. In case of (CH₃)₂SO(OH)]⁺SbF₆]^– a single‐crystal X‐ray structure analysis is reported. The salt crystallizes in the orthorhombic space group Pbca with eight formula units per unit cell a = 10.3281(3) Å, b = 12.2111(4) Å, c = 13.9593(4) Å]. The experimental results are discussed together with quantum chemical calculations on the PBE1PBE/6‐311G++(3pd,3df) level of theory.