Competition H(D) kinetic isotope effects in the autoxidation of hydrocarbons

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DOIResolve DOI: http://doi.org/10.1021/ja511434j
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TypeArticle
Journal titleJournal of the American Chemical Society
ISSN0002-7863
Volume137
Issue1
Pages9497; # of pages: 4
SubjectAbstracting; Atoms; Carrier mobility; Isotopes; Oxidation; Quantum theory; Competition reactions; H-atom abstraction; Hydrogen-atom transfer; Kinetic isotope effects; Peroxyl radical; Quantum-mechanical tunneling; Various substrates; Zero-point energies; Free radical reactions; deuterium; hydrocarbon; hydrogen; isotope; peroxy radical; tetralin derivative; atomic particle; autooxidation; chemical reaction kinetics; chemical structure; intramolecular competition; nuclear magnetic resonance; proton transport; quantum chemistry; reaction analysis
AbstractHydrogen atom transfer is central to many important radical chain sequences. We report here a method for determination of both the primary and secondary isotope effects for symmetrical substrates by the use of NMR. Intramolecular competition reactions were carried out on substrates having an increasing number of deuterium atoms at symmetry-related sites. Products that arise from peroxyl radical abstraction at each position of the various substrates reflect the competition rates for H(D) abstraction. The primary KIE for autoxidation of tetralin was determined to be 15.9 ± 1.4, a value that exceeds the maximum predicted by differences in H(D) zero-point energies (∼7) and strongly suggests that H atom abstraction by the peroxyl radical occurs with substantial quantum mechanical tunneling.
Publication date
PublisherACS Publications
LanguageEnglish
AffiliationNational Research Council Canada; Security and Disruptive Technologies
Peer reviewedYes
NPARC number21275683
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Record identifierfdef3847-1b49-46bf-ba39-2f863984f688
Record created2015-07-14
Record modified2016-05-09
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