Dimethylhydroxyoxosulfonium(VI) Hexafluoridometallates, [(CH 3 ) 2 SO(O X )] + [ M F 6 ] – ( X = H, D; M = As, Sb)

Dimethylsulfone reacts in the binary superacidic systems X F/ M F 5 ( X = H, D; M = As, Sb) under the formation of the corresponding salts of the type [(CH 3 ) 2 SO(O X )] + [ M F 6 ] – . The salts are characterized by low temperature vibrational spectroscopy. In case of [(CH 3 ) 2 SO(OH)] + [SbF 6 ] – 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.