Structural Elucidation of C6H4+. Using Chemical Reaction Monitoring: Charge Transfer Versus Bond Forming Reactions

Mass spectrometry is a powerful tool but when used on its own, without specific activation of ions, the ion mass is the single observable and the structural information is absent. One way of retrieving this information is by using ion-molecule reactions. We propose a general method to disentangle isomeric structures by combining mass spectrometry, tunable synchrotron light source, and quantum-chemistry calculations. We use reactive chemical monitoring technique, which consists in tracking reactivity changes as a function of photoionization energy i. e. the ionic structure. We illustrate the power of this technique with charge transfer reactions of C6H4+. isomers with allene and propyne and discuss its universal applicability. Furthermore, we emphasize the special reactivity characteristics of distonic ions, where strong charge transfer reactivity but very limited reactivity involving bond formation and following cleavages were observed and attributed to the unconventional ortho-benzyne distonic cation.

Automated summary

The article introduces a method to retrieve structural information by using ion-molecule reactions, and uses charge transfer reactions of C6H4+ isomers as an example to illustrate the universal applicability of this method. Furthermore, it emphasizes the special reactivity characteristics of distonic ions.