Experimental Evidence for Heavy-Atom Tunneling in the Ring-Opening of Cyclopropylcarbinyl Radical from Intramolecular 12C/13C Kinetic Isotope Effects Metadata
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- Main Title Experimental Evidence for Heavy-Atom Tunneling in the Ring-Opening of Cyclopropylcarbinyl Radical from Intramolecular 12C/13C Kinetic Isotope Effects
Author: Gonzalez-James, Ollie M.Creator Type: PersonalCreator Info: Texas A & M University
Author: Zhang, XueCreator Type: PersonalCreator Info: University of North Texas
Author: Datta, AyanCreator Type: PersonalCreator Info: University of North Texas
Author: Hrovat, David A.Creator Type: PersonalCreator Info: University of North Texas
Author: Singleton, Daniel A.Creator Type: PersonalCreator Info: Texas A & M University
Author: Borden, Weston T.Creator Type: PersonalCreator Info: University of North Texas
Name: American Chemical SocietyPlace of Publication: [Washington, D.C.]
- Creation: 2010-08-19
- Content Description: Article on experimental evidence for heavy-atom tunneling in the ring-opening of cyclopropylcarbinyl radical from intramolecular 12C/13C kinetic isotope effects.
- Physical Description: 2 p.
- Keyword: tunneling
- Keyword: kinetic isotope effects
- Keyword: chemical reactions
- Journal: Journal of the American Chemical Society, 2010, Washington D.C.: American Chemical Society, pp. 2548-12549
- Publication Title: Journal of the American Chemical Society
- Volume: 132
- Page Start: 12548
- Page End: 12549
- Pages: 2
- Peer Reviewed: True
Name: UNT Scholarly WorksCode: UNTSW
Name: UNT College of Arts and SciencesCode: UNTCAS
- Rights Access: public
- DOI: 10.1021/ja1055593
- Archival Resource Key: ark:/67531/metadc71805
- Academic Department: Chemistry
- Display Note: Reprinted with permission from the Journal of the American Chemical Society. Copyright 2010 American Chemical Society.
- Display Note: Abstract: The intramolecular 13C kinetic isotope effects for the ring-opening of cyclopropylcarbinyl radical were determined over a broad temperature range. The observed isotope effects are unprecedentedly large, ranging from 1.062 at 80 °C to 1.163 at -100 °C. Semiclassical calculations employing canonical variational transition-state theory drastically underpredict the observed isotope effects, but the predicted isotope effects including tunneling by a small-curvature tunneling model match well with experiment. These results and a curvature in the Arrhenius plot of the isotope effects support the recently predicted importance of heavy-atom tunneling in cyclopropylcarbinyl ring-opening.