Kinetic applications of electron paramagnetic resonance spectroscopy. II. Self-reactions of N-alkyl nitroxides and N-phenyl nitroxide

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DOIResolve DOI: http://doi.org/10.1021/ja00753a037
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TypeArticle
Journal titleJournal of the American Chemical Society
ISSN0002-7863
Volume93
Issue24
Pages65516555; # of pages: 5
AbstractThe self-reactions of methyl, isopropyl, tert-butyl, and phenyl nitroxides in solution have been examined by epr spectroscopy. The reaction is a disproportionation to yield a hydroxylamine and a nitroso compound: 2RNHO· → RNHOH + RNO. Rate constants for this reaction have been measured in several solvents. In benzene at 25° the rate constants are in the range 4 × 107 to 3 × 106 M-1 sec-1. For R = phenyl and R = tert-butyl the reaction was shown to be reversible and the equilibrium constants were measured over a range of temperature. The measured enthalpy change for the reaction with R = tert-butyl is in good agreement with that calculated (for R = CH3) from the heats of formation of the various species involved. Evidence is presented for hydrogen bonding of methyl nitroxide in methanol. The rate constant for the slow conversion of phenyl nitroxide to azoxybenzene has also been measured over a range of temperature in benzene.
Publication date
LanguageEnglish
AffiliationNational Research Council Canada (NRC-CNRC)
Peer reviewedYes
NPARC number21276710
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Record identifierc283ecce-5503-4c2c-8f14-0de25da501ad
Record created2015-10-13
Record modified2016-05-09
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