The effects of intramolecular hydrogen bonding on the reactivity of phenoxyl radicals in model systems
Michael Lesslie, Andrii Piatkivskyi, John Lawler, Travis R Helgren, Sandra Osburn, Richard AJ O'Hair, Victor Ryzhov
INTERNATIONAL JOURNAL OF MASS SPECTROMETRY | ELSEVIER | Published : 2015
The effects of hydrogen bonding and spin density at the oxygen atom on the gas-phase reactivity of phenoxyl radicals were investigated experimentally and theoretically in model systems and the dipeptide LysTyr. Gas-phase ion-molecule reactions were carried out between radical cations of several aromatic nitrogen bases with the neutrals nitric oxide and n-propyl thiol. Reactivity of radical cations 4-6 correlated with the spin density. The possibility of hydrogen bonding was explored in compounds which allowed four-, five-, and six-membered rings to be formed between the protonated nitrogen and the phenoxyl oxygen, while possessing similar spin density at the oxygen atom. The N -H⋯O• bond len..View full abstract
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This work was supported by the Department of Chemistry and Biochemistry, Northern Illinois University. The authors thank Prof. Thomas R. Gilbert, Northern Illinois University, for performing NBO and QTAIM calculations. RAJO thanks the ARC CoE for support.