Protonation Isomer Specific Ion-Molecule Radical Reactions

J Am Chem Soc. 2023 Jul 19;145(28):15024-15029. doi: 10.1021/jacs.3c02552. Epub 2023 Jun 20.

Abstract

Through a combination of ion-mobility filtering and laser-equipped quadrupole ion-trap mass spectrometry, the gas-phase reaction kinetics of two protonation isomers of the distonic-radical quinazoline cation are independently measured with ethylene. For these radical addition reactions, protonation site variations drive significant changes in nearby radical reactivity, and this is primarily due to through-space electrostatic effects. Furthermore, quantum chemical methods specifically designed for calculating long-range interactions, such as double-hybrid density functional theory, are required to rationalize the experimentally measured difference in reactivity.