Gas‐phase fluorine migration reactions in the radical cations of pentafluorosulfanylbenzene (Aryl―SF5) and benzenesulfonyl fluoride (Aryl―SO2F) derivatives and in the 2,5‐xylylfluoroiodonium ion |
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| Authors: | Ying Gao Hao‐Yang Wang Xiang Zhang Jia‐Shun Cheng Fang Zhang Yin‐Long Guo |
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| Affiliation: | 1. Shanghai Mass Spectrometry Center, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, , Shanghai, China;2. Department of Applied Chemistry, Zhejiang Gongshang University, , Hangzhou, China;3. State Key Laboratory of Organometallics Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, , Shanghai, China |
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| Abstract: | The gas‐phase reactions of Aryl―SF5·+ and Aryl―SO2F·+ have been studied with the electron ionization tandem mass spectrometry. Such reactions involve F‐atom migration from the S‐atom to the aryl group affording the product ion Aryl―F·+ by subsequent expulsion of SF4 or SO2, respectively. Especially, the 4‐pentafluorosulfanylphenyl cation 4‐SF5C6H4+ (m/z 203) from 4‐NO2C6H4SF5·+ by loss of ·NO2 could occur multiple F‐atom migration reactions to the product ion C6H4F3+ (m/z 133) by loss of SF2 in the MS/MS process. The gas‐phase reactions of 2,5‐xylylfluoroiodonium (pXyl―I+F, m/z 251) have also been studied using the electrospray tandem mass spectrometry, which involve a similar F‐atom migration process from the I‐atom to the aryl group giving the radical cation of 2‐fluoro‐p‐xylene (or its isomer 4‐fluoro‐m‐xylene, m/z 124) by reductive elimination of an iodine atom. All these gas‐phase F‐atom migration reactions from the heteroatom to the aryl group led to the aryl―F coupling product ions with a new formed CAryl―F bond. Density functional theory calculations were performed to shed light on the mechanisms of these reactions. Copyright © 2014 John Wiley & Sons, Ltd. |
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| Keywords: | fluorine migration reaction pentafluorosulfanylbenzene benzenesulfonyl fluoride F‐λ 3‐iodanes tandem mass spectrometry |
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