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Dissecting the Flash Chemistry of Electrogenerated Reactive Intermediates by Microdroplet Fusion Mass Spectrometry
Author(s) -
Hu Jun,
Wang Ting,
Zhang WenJun,
Hao Han,
Yu Qiao,
Gao Hang,
Zhang Nan,
Chen Yun,
Xia XingHua,
Chen HongYuan,
Xu JingJuan
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202106945
Subject(s) - reactive intermediate , chemistry , mass spectrometry , microsecond , reaction intermediate , photochemistry , combinatorial chemistry , ion , organic chemistry , chromatography , physics , astronomy , catalysis
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.