Identification of the Electrogenerated Hidden Nitrenium Ions by In Situ Mass Spectrometry

The identification of the electrogenerated reactive intermediates is essential for an in-depth understanding of the electroredox processes. Although various short-lived intermediates are well characterized by coupling electrochemistry with mass spectrometry (EC/MS), many electrogenerated transient species (τ < 1 μs) are still rarely captured by the currently available EC/MS approaches. Here, we present a low-delay coupling device, which was constructed by decorating a microelectrode into the front tip of a microsized ion emitter. For the first time, the in situ detection of a previously hidden intermediate, i.e., the transient nitrenium ion of carbazole (τ = 333 ns), was achieved. The electrochemical generation of indole nitrenium ion, whose half-life is estimated to be shorter compared to the carbazole nitrenium ion due to less resonance stabilization, was also confirmed by direct observation. This clog-free microelectrode/ion emitter is cheap and easy to fabricate and offers a general and powerful approach to monitoring the fast reactions of electrogenerated reactive intermediates. We believe that our integrated EC/MS approach holds substantial potential for broad applicability, particularly in probing the intricate and ultrafast electroredox processes occurring at the electrode-solution interface.