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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Title

  • Main Title Experimental Evidence for Heavy-Atom Tunneling in the Ring-Opening of Cyclopropylcarbinyl Radical from Intramolecular 12C/13C Kinetic Isotope Effects

Creator

  • Author: Gonzalez-James, Ollie M.
    Creator Type: Personal
    Creator Info: Texas A & M University
  • Author: Zhang, Xue
    Creator Type: Personal
    Creator Info: University of North Texas
  • Author: Datta, Ayan
    Creator Type: Personal
    Creator Info: University of North Texas
  • Author: Hrovat, David A.
    Creator Type: Personal
    Creator Info: University of North Texas
  • Author: Singleton, Daniel A.
    Creator Type: Personal
    Creator Info: Texas A & M University
  • Author: Borden, Weston T.
    Creator Type: Personal
    Creator Info: University of North Texas

Publisher

  • Name: American Chemical Society
    Place of Publication: [Washington, D.C.]

Date

  • Creation: 2010-08-19

Language

  • English

Description

  • 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.

Subject

  • Keyword: tunneling
  • Keyword: kinetic isotope effects
  • Keyword: chemical reactions

Source

  • Journal: Journal of the American Chemical Society, 2010, Washington D.C.: American Chemical Society, pp. 2548-12549

Citation

  • Publication Title: Journal of the American Chemical Society
  • Volume: 132
  • Page Start: 12548
  • Page End: 12549
  • Pages: 2
  • Peer Reviewed: True

Collection

  • Name: UNT Scholarly Works
    Code: UNTSW

Institution

  • Name: UNT College of Arts and Sciences
    Code: UNTCAS

Rights

  • Rights Access: public

Resource Type

  • Article

Format

  • Text

Identifier

  • DOI: 10.1021/ja1055593
  • Archival Resource Key: ark:/67531/metadc71805

Degree

  • Academic Department: Chemistry

Note

  • 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.