Capture and Identification of the Electrogenerated Picosecond Intermediates by Mass Spectrometry

•In-situ generation of electrochemical intermediates during electrospray ionization•The first mass spectrometric identification of picosecond nitrenium/oxenium ions•The first direct observation of the long-sought discrete glycosyl oxocarbenium ion•Cationic intermediates are stabilized in the positively charged microdroplets