Abstract
The e.p.r. spectrum of thiyl radicals is obtained when dilute solutions of aliphatic mercaptans are photolyzed in a xenon matrix at 77 °K. No proton hyperfine structure is observed at low concentrations of thiol but it appears at higher concentrations due to the reaction of hot hydrogen atoms with solute mercaptan molecules. When small amounts of the thiols are dissolved in glassy hydrocarbon matrices such as 3-methylpentane, there is produced after photolysis hyperfine structure characteristic of the solvent as well as the thiyl resonance. The e.s.r. absorption due to the solvent species disappears when the matrix is warmed a few degrees above 77 °K but thiyl radicals are stable up to the melting point of the glass. The corresponding γ-irradiated glasses do not give thiyl absorption, but two other species are produced along with solvent radicals. No thiyl radicals are observed following radiolysis, or upon photo-bleaching the new species. The spatial distribution of the neutral radicals in the glasses is discussed in view of these results.
Publisher
Canadian Science Publishing
Subject
Organic Chemistry,General Chemistry,Catalysis
Cited by
17 articles.
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