Premium
Detection of the Short‐Lived Radical Cation Intermediate in the Electrooxidation of N , N ‐Dimethylaniline by Mass Spectrometry
Author(s) -
Brown Timothy A.,
Chen Hao,
Zare Richard N.
Publication year - 2015
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.201506316
Subject(s) - dimethylaniline , mass spectrometry , electrochemistry , chemistry , electrode , desorption , analytical chemistry (journal) , electrospray ionization , microsecond , radical ion , photochemistry , ion , chromatography , organic chemistry , adsorption , physics , astronomy
The N , N ‐dimethylaniline (DMA) radical cation DMA .+ , a long‐sought transient intermediate, was detected by mass spectrometry (MS) during the electrochemical oxidation of DMA. This was accomplished by coupling desorption electrospray ionization (DESI) MS with a waterwheel working electrode setup to sample the surface of the working electrode during electrochemical analysis. This study clearly shows that DESI‐based electrochemical MS is capable of capturing electrochemically generated intermediates with half‐lives on the order of microseconds, which is 4–5 orders of magnitude faster than previously reported electrochemical mass spectrometry techniques.