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

The S–π interaction between sulfur atom(s) and aromatic ring prevails in chemical and biochemical processes. The thermal gas-phase reactions of the Sn+ (n = 1–3) ions with benzene have been explored by using Quadrupole-Ion Trap (Q-IT) mass spectrometry complemented by quantum chemical calculations....

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Bibliographic Details
Published in:Physical chemistry chemical physics : PCCP 2021-08, Vol.23 (32), p.17512-17520
Main Authors: Yu, Mincheng, Ge, Xin, Zhou, Shaodong
Format: Article
Language:English
Subjects:
Aromatic compounds
Benzene
Charge transfer
Chemical reactions
Hydrocarbons
Mass spectrometry
Origins
Quadrupoles
Quantum chemistry
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Summary:The S–π interaction between sulfur atom(s) and aromatic ring prevails in chemical and biochemical processes. The thermal gas-phase reactions of the Sn+ (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 Sn+/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.
ISSN:1463-9076
1463-9084
DOI:10.1039/d1cp01959g