| Download | - View accepted manuscript: Competition H(D) kinetic isotope effects in the autoxidation of hydrocarbons (PDF, 748 KiB)
|
|---|
| DOI | Resolve DOI: https://doi.org/10.1021/ja511434j |
|---|
| Author | Search for: Muchalski, Hubert; Search for: Levonyak, Alexander J.; Search for: Xu, Libin; Search for: Ingold, Keith U.1; Search for: Porter, Ned A. |
|---|
| Affiliation | - National Research Council of Canada. Security and Disruptive Technologies
|
|---|
| Format | Text, Article |
|---|
| Subject | Abstracting; 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 |
|---|
| Abstract | 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 (∼7) and strongly suggests that H atom abstraction by the peroxyl radical occurs with substantial quantum mechanical tunneling. |
|---|
| Publication date | 2015-01-02 |
|---|
| In | |
|---|
| Language | English |
|---|
| Peer reviewed | Yes |
|---|
| NPARC number | 21275683 |
|---|
| Export citation | Export as RIS |
|---|
| Report a correction | Report a correction (opens in a new tab) |
|---|
| Record identifier | fdef3847-1b49-46bf-ba39-2f863984f688 |
|---|
| Record created | 2015-07-14 |
|---|
| Record modified | 2020-06-04 |
|---|
