Kinetic applications of electron paramagnetic resonance spectroscopy. 37. The reaction of bis(trifluoromethyl) nitroxide with toluene. Evidence for quantum mechanical tunneling in an intermolecular hydrogen atom abstraction

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DOIResolve DOI: http://doi.org/10.1021/ja00401a030
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TypeArticle
Journal titleJournal of the American Chemical Society
ISSN0002-7863
Volume103
Issue11
Pages30943098; # of pages: 5
AbstractRate constants for hydrogen atom abstraction from toluene and for deuterium abstraction from toluene-d8 by bis(trifluoromethyl) nitroxide in chlorofluorocarbon solvents have been measured by kinetic EPR spectroscopy over a wide range of temperatures. Quantum mechanical tunneling may play a role in this reaction since the Arrhenius preexponential factors are unusually low, AH ≈ AD, = 104 M-1 s-1, and the activation energy difference, ED - EH, is 1-6 kcal/mol, which is unusually large. The O-H bond strength in (CF3)2NOH has been found to be 82.6 kcal/mol by using an EPR equilibrium technique. © 1981 American Chemical Society.
Publication date
LanguageEnglish
AffiliationNational Research Council Canada (NRC-CNRC)
Peer reviewedYes
NPARC number21276611
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Record identifier274ddde6-961c-4e40-8187-958acbf4b7e3
Record created2015-10-13
Record modified2016-05-09
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