Structural Elucidation of C6H4+. Using Chemical Reaction Monitoring: Charge Transfer Versus Bond Forming Reactions. Issue 5 (28th January 2022)

• Record Type: Journal Article
• Authors: Jacovella, Ugo; Rossi, Corentin; Romanzin, Claire; Alcaraz, Christian; Thissen, Roland
• Is Part Of: Chemphyschem. Volume 23:Issue 5(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-01-28
• Subjects: charge transfer -- distonic radical cations -- Ion-molecule reaction -- mass spectrometry -- structure elucidation; Chemistry, Physical and theoretical -- Periodicals; 541.05
• DOI: 10.1002/cphc.202100871
• Languages: English
• ISSNs: 1439-4235

Abstract

Abstract: 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 C6 H4 +. 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. Abstract : Chemical monitoring technique is used to disentangle the structural diversity of a C6 H4 + isomeric mixture. The structural elucidation of C6 H4 + isomers is done by monitoring different structure‐specific ion–molecule reaction channels with propyne and allene, highlighting an abnormally large charge transfer cross section for the distonic ortho ‐benzyne cation together with a surprisingly very weak chemical reactivity.@Ujacovella @ISMOlab_Orsay