Calculations Predict a Large Inverse H/D Kinetic Isotope Effect on the Rate of Tunneling in the Ring Opening of Cyclopropylcarbinyl Radical

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Article on calculations predicting a large inverse H/D kinetic isotope effect on the rate of tunneling in the ring opening of cyclopropylcarbinyl radical.

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2 p.

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Zhang, Xue; Datta, Ayan; Hrovat, David A. & Borden, Weston T., 1943- October 15, 2009.

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Article on calculations predicting a large inverse H/D kinetic isotope effect on the rate of tunneling in the ring opening of cyclopropylcarbinyl radical.

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2 p.

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Abstract: Tunneling rates are expected to decrease exponentially with the square root of the effective tunneling mass. Therefore, on substitution of a heavier for a lighter isotope, the observation of a large kinetic isotope effect (KIE), involving a substantial decrease in rate constant, is a commonly used diagnostic for a large contribution from quantum mechanical tunneling to a reaction. However, in this communication, the authors report the results of calculations that make the opposite prediction about some of the KIEs on the ring opening of cyclopropylcarbinyl radical (1) to 3-butene-1-y1 radical (2) by tunneling at cryogenic temperatures. Substitution of a heavier for a lighter isotope at the radical center (C1) of 1 is calculated to accelerate the rate of tunneling, giving KIEs at this carbon that are inverse. Of particular note is the authors' prediction that substitution of deuterium for both hydrogens at C1 will lead to a nearly 3-fold increase in the rate of reaction at temperatures so low that ring opening proceeds exclusively by tunneling from the lowest vibrational level.

Reprinted with permission from the Journal of the American Chemical Society. Copyright 2009 American Chemical Society.

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  • Journal of the American Chemical Society, 2009, Washington DC: American Chemical Society, pp. 16002-16003

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  • Publication Title: Journal of the American Chemical Society
  • Volume: 131
  • Page Start: 16002
  • Page End: 16003
  • Peer Reviewed: Yes

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The Scholarly Works Collection is home to materials from the University of North Texas community's research, creative, and scholarly activities and serves as UNT's Open Access Repository. It brings together articles, papers, artwork, music, research data, reports, presentations, and other scholarly and creative products representing the expertise in our university community.** Access to some items in this collection may be restricted.**

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  • October 15, 2009

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  • Jan. 31, 2012, 10:30 a.m.

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  • Feb. 26, 2014, 10:31 a.m.

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Zhang, Xue; Datta, Ayan; Hrovat, David A. & Borden, Weston T., 1943-. Calculations Predict a Large Inverse H/D Kinetic Isotope Effect on the Rate of Tunneling in the Ring Opening of Cyclopropylcarbinyl Radical, article, October 15, 2009; [Washington, DC]. (digital.library.unt.edu/ark:/67531/metadc71808/: accessed February 25, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.