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

DOI	Resolve DOI: https://doi.org/10.1021/ja00401a030
Author	Search for: Malatesta, V.¹; Search for: Ingold, K. U.¹
Name affiliation	National Research Council of Canada
Format	Text, Article
Journal title	Journal of the American Chemical Society
ISSN	0002-7863
Volume	103
Issue	11
Pages	3094–3098
Abstract	Rate 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	1981
Language	English
Peer reviewed	Yes
NPARC number	21276611
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Record identifier	274ddde6-961c-4e40-8187-958acbf4b7e3
Record created	2015-10-13
Record modified	2020-03-13