TOLUENIUM AND OTHER GASEOUS METHYLBENZENIUM IONS: COMPLEX INTERPLAY OF PROTONATED ARENES AND CYCLO-OLEFINS

Abstract

The development of the current knowledge of the gas-phase chemistry of protonated methylbenzenes, such as toluenium, xylenium and mesitylenium ions, their higher congeners as well as of their mostly cyclo-olefinic isomers by mass spectrometric methodology is presented. Starting from the observation of the characteristic expulsion of dihydrogen from metastable C₇ H₉ ⁺ ions, which is associated with the release of large amounts of kinetic energy, and the composite C- and H-scrambling prior to the loss of methane, in particular, insights into the isomerization scenario of various isomeric C₇ H₉ ⁺ , C₈ H₁₁ ⁺ , and C₉ H₁₃ ⁺ ions, based on a large variety of independent techniques, are discussed. Besides isotope labeling and metastable ion methodology, these include flowing afterglow mass spectrometry, gas-phase titration and infrared spectroscopy of mass-selected ions. The particularly complex energy hypersurface of isomerizing and fragmenting toluenium ions, which has been elaborated in various reports over the years, is presented in a combined way to assess the role of protonated cycloheptatriene, norbornadiene, and 6-methylfulvene as well as a number of further C₇ H₉ ⁺ isomers. The formation and nature of C₇ H₉ ⁺ ions generated by fragmentation of various hydrocarbon precursors, such as monoterpenes and adamantane, is also addressed. The contribution of infrared multiphoton dissociation spectroscopy (IRMPD) and tagged-ion infrared photodissociation (IRPD) of the gaseous C₇ H₉ ⁺ ions as compared to the wealth of previous understanding of their chemistry is commented on as well. Finally, remarkable parallels of the gas-phase chemistry of methylbenzenium ions and the role of such species within the cavities of acidic zeolite catalysts in the course of the industrially important methanol-to-hydrocarbon reaction are discussed. © 2020 John Wiley & Sons Ltd. Mass Spec Rev.

Keywords: IR spectroscopy of gaseous ions; MTH reaction; cyclo-olefins, protonated; gas-phase ion chemistry; isomerization; kinetic energy release; metastable ions; methylbenzenes, protonated; scrambling, H and C; titration, gas phase; toluenium ions; xylenium ions.