Reactivity of “Ligand-Free” Au⁺: C–H and C–C Activation versus π Coordination

[(Me2S)­Au]+ cations, generated from (Me2S)­AuCl and AgSbF6 in dichloromethane at 0–20 °C, serve as sources of solvated Au+ (alongside unreactive [Au­(SMe2)2]+), which reacts with the methyl-substituted arenes C6Me6–nHn (n = 0–2) with C–H bond cleavage to give the sulfonium salts [C6Me5–nHnCH2SMe2]+. There was no evidence for arene π coordination to Au+ or for the formation of σ-bonded Au–benzyl species. Surprisingly, the reaction of Au+ with CH2Ar2 leads to C–C bond cleavage (Ar = 2,4,6-C6H2Me3). The reactions are highly selective for benzylic C–H and C–C bonds, whereas metalation of the arene ring is not observed.