Ion-molecule reactions of Me₂S₂ with a wide range of aliphatic carbanions differing by structure and proton affinity values have been studied in the gas phase using mass spectrometry techniques and DFT calculations. The analysis of the spectra shows a variety of product ions formed via different reaction mechanisms, depending on the structure and proton affinity of the carbanion. Product ions of thiophilic reaction (m/z 47), S_N2 (m/z 79), and E2 elimination – addition sequence of reactions (m/z 93) can be observed. Primary products of thiophilic reaction can undergo subsequent S_N2 and proton transfer reactions. Gibbs free energy profiles calculated for experimentally observed reactions using PBE0/6-311+G(2d,p) method show good agreement with experimental results.

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已在气相中使用质谱技术和DFT计算研究了Me ₂ S ₂与结构和质子亲和力值不同的各种脂族碳负离子的离子分子反应。光谱分析表明，取决于碳负离子的结构和质子亲和力，通过不同的反应机理形成的各种产物离子。可以观察到亲硫反应的产物离子（m / z 47），S _N 2（m / z 79）和E2的消除–反应的添加顺序（m / z 93）。亲硫反应的主要产物可以经历随后的S _N2，与质子转移反应。使用PBE0 / 6-311 + G（2d，p）方法为实验观察到的反应计算的吉布斯自由能谱显示出与实验结果良好的一致性。

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