Kinetic applications of electron paramagnetic resonance spectroscopy. XXII. Dialkylaminothiyl radicals

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DOIResolve DOI: http://doi.org/10.1021/ja00418a032
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TypeArticle
Journal titleJournal of the American Chemical Society
ISSN0002-7863
Volume98
Issue2
Pages520523; # of pages: 4
AbstractThe equilibria between 2,2,6,6-tetramethylpiperidyl-1-thiyl and diisopropylaminothiyl and the corresponding bis(dialkylamino) disulfides have been examined by EPR spectroscopy: R2NSSNR2 ⇌ 2R2NS (k1, k-1). Within experimental error, the equilibrium constants are the same for both radicals (ΔS = 23 ± 4 gibbs/mol, ΔH = 27 ± 2 kcal/mol), as are the rate constants for disulfide decomposition and radical combination which can be represented, respectively, by log (k1/sec-1) = 16.8 - 31/θ and log (k-1/M-1 sec-1) = 11.8 - 4.0/0, where θ = 2.3RT kcal/mol. These radicals were generated in solution both thermally and photochemically, but photolysis in solid matrices at low temperatures gives some N-S bond scission. Dialkylaminothiyl radicals are unreactive toward a variety of molecular substrates. The first sulfur analogue of an iminoxy radical, diphenyliminothiyl, has been generated by photolysis of the corresponding disulfide. Its EPR parameters are g = 2.0152, aN = 18.16 G.
Publication date
LanguageEnglish
AffiliationNational Research Council Canada (NRC-CNRC)
Peer reviewedYes
NPARC number21276736
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Record identifiera20b1185-b0bb-44d5-9d25-28bdaff260c5
Record created2015-10-13
Record modified2016-05-09
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