Formation and reactivity of pyridylperoxyl radicals in solution

Z. B. Alfassi, G. I. Khaikin, P. Neta

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9 Scopus citations

Abstract

2-Pyridyl radicals were produced by the reaction of 2-chloro- or 2-bromopyridine with solvated electrons (k approximately 1010 L mol-1 s-1) and reacted rapidly with oxygen (k = 2.2 × 109 L mol-1 s-1) to produce the 2-pyridylperoxyl radical. This radical exhibits optical absorption in the visible range, with λmax at 440 nm. 2-Pyridylperoxyl radical is a fairly strong oxidant, which reacts with 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonate ion) (ABTS), chlorpromazine, and 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid (Trolox C) by one-electron oxidation. The rate constants k for these reactions, determined from the rate of formation of the one-electron oxidation as a function of substrate concentration, vary between 2 × 106 and 2 × 109 L mol-1 s-1 in various mixtures. For each substrate, a good correlation was found between log k and the cohesive pressure of the solvent or solvent mixture, as found before for CCI3O2 radical reactions in nearly neat solvents. 3-Bromo, 3-chloro- and 4-chloropyridine also reacted rapidly with solvated electrons, but their radical anions underwent protonation on the nitrogen in competition with the dehalogenation process. Therefore, no pyridylperoxyl radicals were formed from these species in aqueous solutions and only partial yield was found in neat methanol.

Original languageEnglish
Pages (from-to)4544-4548
Number of pages5
JournalJournal of Physical Chemistry
Volume99
Issue number13
DOIs
StatePublished - 1 Jan 1995
Externally publishedYes

ASJC Scopus subject areas

  • Engineering (all)
  • Physical and Theoretical Chemistry

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