Dissecting the Flash Chemistry of Electrogenerated Reactive Intermediates by Microdroplet Fusion Mass Spectrometry. Issue 34 (13th July 2021)

• Record Type: Journal Article
• Authors: Hu, Jun; Wang, Ting; Zhang, Wen‐Jun; Hao, Han; Yu, Qiao; Gao, Hang; Zhang, Nan; Chen, Yun; Xia, Xing‐Hua; Chen, Hong‐Yuan; Xu, Jing‐Juan
• Is Part Of: Angewandte Chemie international edition. Volume 60:Issue 34(2021)
• Page Start: 18494
• Page End: 18498
• Publication Date: 2021-07-13
• Subjects: electrospray ionization -- mass spectrometry -- microdroplet reaction -- reactive radical intermediate; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202106945
• Languages: English
• ISSNs: 1433-7851

Abstract

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 : Microreactor on the fly: A special microreactor that permits mass spectrometric probing the flash chemistry of electrogenerated reactive intermediates was demonstrated based on collision mixing of electrosprayed microdroplets, which employed a theta‐glass capillary integrated with carbon bipolar electrodes to produce short‐lived intermediates in situ.