Related Experiment Video
Updated: Mar 8, 2026

Thermochemical Studies of NiII and ZnII Ternary Complexes Using Ion Mobility-Mass Spectrometry
Published on: June 8, 2022
Competitive benzyl cation transfer and proton transfer: collision-induced mass spectrometric fragmentation of
1Deparment of Chemistry, Zhejiang University, 38 Zheda Road, Hangzhou, 310027, Zhejiang, China.
Abstract:
Collision-induced dissociation of protonated N,N-dibenzylaniline was investigated by electrospray tandem mass spectrometry. Various fragmentation pathways were dominated by benzyl cation and proton transfer. Benzyl cation transfers from the initial site (nitrogen) to benzylic phenyl or aniline phenyl ring. The benzyl cations transfer to the two different sites, and both result in the benzene loss combined with 1,3-H shift. In addition, after the benzyl cation transfers to the benzylic phenyl ring, 1,2-H shift and 1,4-H shift proceed competitively to trigger the diphenylmethane loss and aniline loss, respectively. Deuterium labeling experiments, substituent labeling experiments and density functional theory calculations were performed to support the proposed benzyl cation and proton transfer mechanism. Overall, this study enriches the knowledge of fragmentation mechanisms of protonated N-benzyl compounds. Copyright © 2017 John Wiley & Sons, Ltd.
Related Concept Videos
Chemical Ionization (CI) Mass Spectrometry
Mass Spectrometry: Aromatic Compound Fragmentation
Electrophilic Aromatic Substitution: Nitration of Benzene
Mass Spectrometry of Amines
NMR Spectroscopy of Benzene Derivatives
Mass Spectrometry: Amine Fragmentation
In amines, the number of nitrogen atoms affects the mass of the molecular ion, which is described by the nitrogen rule of mass spectrometry. This rule states that a compound containing a single...

