Collision‐induced dissociation of negative ions in the gas phase: [Aryl S] − , [aryl SO] − and [aryl SO 2 ] −

Collision‐induced dissociation of the ions [ArS] − , [ArSO] − and [ArSO 2 ] − has uncovered a rich and varied ion chemistry. The major fragmentations of [ArS] − are complex and occur without prior ring hydrogen scrambling: for example, [C 6 H 5 S] − →[C 2 HS] − and [HS] − ; [ p ‐CD 3 C 6 H 4 S] − →[C 6 H 4 S] − ˙, [CD 3 C 4 S] − and [C 2 HS] − . In contrast, all decompositions of [C 6 H 5 CH 2 S] − are preceded by specific benzylic and phenyl hydrogen interchange reactions. [ArSO 2 ] − and [ArSO 2 ] − ions undergo rearrangement, e.g. [C 6 H 5 SO] − →[C 6 H 5 O] − and [C 6 H 5 S] − ; [C 6 H 5 SO 2 ] − →[C 6 H 5 O] − . The ion [C 6 H 5 CH 2 SO] − eliminates water, this decomposition is preceded by benzylic and phenyl hydrogen exchange.