Journal article

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

Abstract

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..

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University of Melbourne Researchers