1. Dissecting the Flash Chemistry of Electrogenerated Reactive Intermediates by Microdroplet Fusion Mass Spectrometry.
- Author
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Hu, Jun, Wang, Ting, Zhang, Wen‐Jun, Hao, Han, Yu, Qiao, Gao, Hang, Zhang, Nan, Chen, Yun, Xia, Xing‐Hua, Chen, Hong‐Yuan, and Xu, Jing‐Juan
- Subjects
INTERMEDIATES (Chemistry) ,MASS spectrometry ,MICRODROPLETS ,CARBON electrodes ,PHENOTHIAZINE ,RADICAL ions ,RADICAL cations - Abstract
A novel mass spectrometric method for probing the flash chemistry of electrogenerated reactive intermediates was developed based on rapid collision mixing of electrosprayed microdroplets by using a theta‐glass capillary. The two individual microchannels of the theta‐glass capillary are asymmetrically or symmetrically fabricated with a carbon bipolar electrode to produce intermediates in situ. Microdroplets containing the newly formed intermediates collide with those of the invoked reactants at sub‐10 microsecond level, making it a powerful tool for exploring their ultrafast initial transformations. As a proof‐of‐concept, we present the identification of the key radical cation intermediate in the oxidative dimerization of 8‐methyl‐1,2,3,4‐tetrahydroquinoline and also the first disclosure of previously hidden nitrenium ion involved reaction pathway in the C−H/N−H cross‐coupling between N,N′‐dimethylaniline and phenothiazine. [ABSTRACT FROM AUTHOR]
- Published
- 2021
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