Capture of Electrochemically Generated Fleeting Carbazole Radical Cations and Elucidation of Carbazole Dimerization Mechanism by Mass Spectrometry

Chengyuan Liu; Qi Wang; Brian E Hivick; Yongling Ai; Pier Alexandre Champagne; Yang Pan; Hao Chen

doi:10.1021/acs.analchem.0c01223

Capture of Electrochemically Generated Fleeting Carbazole Radical Cations and Elucidation of Carbazole Dimerization Mechanism by Mass Spectrometry

Anal Chem. 2020 Dec 1;92(23):15291-15296. doi: 10.1021/acs.analchem.0c01223. Epub 2020 Oct 21.

Authors

Chengyuan Liu^{1

2}, Qi Wang¹, Brian E Hivick³, Yongling Ai¹, Pier Alexandre Champagne¹, Yang Pan², Hao Chen^{1

3}

Affiliations

¹ Department of Chemistry & Environmental Science, New Jersey Institute of Technology, Newark, New Jersey 07102, United States.
² National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029, China.
³ Department of Chemistry & Biochemistry, Ohio University, Athens, Ohio 45701, United States.

PMID: 33084312
DOI: 10.1021/acs.analchem.0c01223

Abstract

The capture of reactive intermediates is important for the elucidation of reaction mechanisms. We report the first observation of electrochemically generated, short-lived radical cations of carbazole (t_1/2 ≈ 97 μs) and two N-substituted carbazole derivatives by mass spectrometry. In addition, online investigation of the reactivity of electrochemically generated carbazole radical cations supports that the carbazole dimerization mechanism involves the reaction of one radical cation with one neutral molecule rather than the previously proposed coupling of two radical cations.

Publication types

Research Support, U.S. Gov't, Non-P.H.S.