Protonation Isomer Specific Ion-Molecule Radical Reactions

Through a combination of ion-mobility filtering and laser-equippedquadrupole ion-trap mass spectrometry, the gas-phase reactionkinetics of two protonation isomers of the distonic-radical quinazolinecation are independently measured with ethylene. For these radicaladdition reactions, protonation site variations drive significantchanges in nearby radical reactivity, and this is primarily due tothrough-space electrostatic effects. Furthermore, quantum chemicalmethods specifically designed for calculating long-range interactions,such as double-hybrid density functional theory, are required to rationalizethe experimentally measured difference in reactivity.

Automated summary

The gas-phase reaction kinetics of the distonic-radical quinazoline cation's two protonation isomers are independently measured using ion-mobility filtering and laser-equipped quadrupole ion-trap mass spectrometry. The variation in protonation sites significantly affects nearby radical reactivity due to through-space electrostatic effects. Quantum chemical methods, such as double-hybrid density functional theory, are required to explain the experimentally measured difference in reactivity.