Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 137, Issue 1, Pages 94-97Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja511434j
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Funding
- National Science Foundation [NSF-CHE1057500]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1057500] Funding Source: National Science Foundation
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Hydrogen 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 (similar to 7) and strongly suggests that H atom abstraction by the peroxyl radical occurs with substantial quantum mechanical tunneling.
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