On the Electronic Origins of the Different Behaviors of S+ and S2+/2+ in Methane Activation.

The thermal gas‐phase reactions of S+, S2+ and S22+ with methane have been explored by using quadrupole‐ion trap (Q‐IT) mass spectrometry complemented by quantum chemical calculations. In contrast to the reactiveness of the S+/CH4 and S22+/CH4 couples as identified by experiment and computation, respectively, the S2+/CH4 couple is inert at ambient temperature. Interestingly, the hydrogen‐atom transfer (HAT) prevails for S+/CH4 and proton‐coupled electron transfer (PCET) for S2+/CH4, while both PCET and hydride transfer (HT) are accessible for S22+/CH4. Multiple factors matter for these processes. The electronic origins of the different reactivities of the three ions have been interrogated. [ABSTRACT FROM AUTHOR]