Formation of Protonated ortho-Quinonimide from ortho-Iodoaniline in the Gas Phase by a Molecular-Oxygen-Mediated, ortho-Isomer-Specific Fragmentation Mechanism

Upon collisional activation under mass spectrometric conditions, protonated 2-, 3-, and 4-iodoanilines lose an iodine radical to generate primarily dehydroanilinium radical cations (m/z 93), which are the distonic counterparts of the conventional molecular ion of aniline. When briefly accumulated in the Trap region of a Triwave cell in a SYNAPT G2 instrument, before being released for ion-mobility separation, these dehydroanilinium cations react readily with traces of oxygen present in the mobility gas to form peroxyl radical cations. Although all three isomeric dehydroanilinium ions showed avid affinity for O2, their reactivities were distinctly different. For example, the product-ion spectra recorded from mass-selected m/z 93 ion from 3- and 4-iodoanilines showed a peak at m/z 125 for the respective peroxylbenzenaminium ion. In contrast, an analogous peak at m/z 125 was absent in the spectrum of the 2-dehydroanilinium ion generated from 2-iodoaniline. Evidently, the 2-peroxylbenzenaminium ion generated from the 2-dehydroanilinium ion immediately loses a OH to form protonated ortho-quinonimide (m/z 108).