Protonation Isomer Specific Ion–Molecule Radical Reactions
Oisin J. Shiels, Samuel J. P. Marlton, Adam J. Trevitt
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.
Topics & Concepts
ChemistryProtonationReactivity (psychology)IonMass spectrometryMoleculeRadical ionPhotochemistryComputational chemistryIon trapOrganic chemistryChromatographyMedicinePathologyAlternative medicineMass Spectrometry Techniques and ApplicationsInsect and Pesticide ResearchRadical Photochemical Reactions