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On the Electronic Origins of the Different Behaviors of S + and S 2 +/2+ in Methane Activation
Author(s) -
Yu Mincheng,
Ruan Jiancheng,
Qian Chao,
Chen Xinzhi,
Ge Xin,
Zhou Shaodong
Publication year - 2020
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.202002907
Subject(s) - chemistry , methane , ion , electron transfer , proton , hydrogen , hydrogen atom , kinetic isotope effect , mass spectrometry , atomic physics , quadrupole , hydride , analytical chemistry (journal) , deuterium , physics , organic chemistry , nuclear physics , alkyl , chromatography
The thermal gas‐phase reactions of S + , S 2 + and S 2 2+ 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 + /CH 4 and S 2 2+ /CH 4 couples as identified by experiment and computation, respectively, the S 2 + /CH 4 couple is inert at ambient temperature. Interestingly, the hydrogen‐atom transfer (HAT) prevails for S + /CH 4 and proton‐coupled electron transfer (PCET) for S 2 + /CH 4 , while both PCET and hydride transfer (HT) are accessible for S 2 2+ /CH 4 . Multiple factors matter for these processes. The electronic origins of the different reactivities of the three ions have been interrogated.