On the origins of the mechanistic variants in the thermal reactions of Sx+ (x = 1-3) with benzene

Abstract

The S-π interaction between sulfur atom(s) and aromatic ring prevails in chemical and biochemical processes. The thermal gas-phase reactions of the S_n⁺ (n = 1-3) ions with benzene have been explored by using Quadrupole-Ion Trap (Q-IT) mass spectrometry complemented by quantum chemical calculations. Charge transfer was found to be the only reaction channel for S₂⁺/C₆H₆, while both charge transfer and bond activation are available for the S⁺/C₆H₆ and S₃⁺/C₆H₆ couples. Upon interrogating the associated electronic origins, multiple factors were found to matter for these processes. In contrast to the σ-type two-center three-electron (2c-3e) S-π hemibond as reported previously, unusual S-π hemibonds were addressed for the S_n⁺/C₆H₆ couples, i.e. the 2c-3e π(S061Eπ) and the three-center three-electron (3c-3e) σ(S₂061Eπ) hemibonds. Such S-π interaction was found to be responsible for the charge transfer processes in S⁺/C₆H₆ and S₂⁺/C₆H₆, but uninvolved in any transformation for S₃⁺/C₆H₆.