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Contrasting behavior of tetracene and perylene in collision‐induced dissociation: a theoretical interpretation
Author(s) -
FleuratLessard Paul,
Pointet Karine,
Milliet Arielle
Publication year - 1999
Publication title -
journal of mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 1076-5174
DOI - 10.1002/(sici)1096-9888(199907)34:7<768::aid-jms833>3.0.co;2-3
Subject(s) - tetracene , chemistry , dissociation (chemistry) , ion , perylene , hydride , collision induced dissociation , molecule , chemical ionization , computational chemistry , photochemistry , mass spectrometry , ionization , tandem mass spectrometry , organic chemistry , metal , chromatography
Dimethyl ether chemical ionization mass spectrometry of polycyclic aromatic hydrocarbons (PAHs) leads to [M + 13] + and [M + 45] + ions. The process leading to these ions is sensitive to the proton affinity of the PAH. Collision‐induced dissociation observations on [M + 45] + ion also show that tetracene has a peculiar reactivity in comparison with perylene, despite the similar physico‐chemical properties of these two molecules. Ab initio calculations were used to establish a potential energy profile for the mechanistic pathway of [M + 13] + and [M + 45] + formation. [M + 45] + ions result from the addition of CH 3 —O—CH 2 + to PAHs. A 1,2‐hydride transfer followed by a 1,4‐proton transfer and a loss of methanol subsequently lead to the formation of [M + 13] + ions. For tetracene, the 1,2‐hydride transfer does not occur, as it would lead to a thermodynamically unstable non‐planar ion. Copyright © 1999 John Wiley & Sons, Ltd.