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Original scientific paper

Deuterium Isotope Effects on the Carbon-13 Chemical Shifts in 2-Substituted-2-Norbornyl Cations

Kenneth L. Servis ; Department of Chemistry, University of Southern California, Los Angeles, California 90089-0744, USA
Edward V. Koh ; Department of Chemistry, University of Southern California, Los Angeles, California 90089-0744, USA
Peter Baine ; Department of Chemistry, University of Southern California, Los Angeles, California 90089-0744, USA

Fulltext: english, pdf (47 MB) pages 679-701 downloads: 238* cite
APA 6th Edition
Servis, K.L., Koh, E.V. & Baine, P. (1992). Deuterium Isotope Effects on the Carbon-13 Chemical Shifts in 2-Substituted-2-Norbornyl Cations. Croatica Chemica Acta, 65 (3), 679-701. Retrieved from https://hrcak.srce.hr/137126
MLA 8th Edition
Servis, Kenneth L., et al. "Deuterium Isotope Effects on the Carbon-13 Chemical Shifts in 2-Substituted-2-Norbornyl Cations." Croatica Chemica Acta, vol. 65, no. 3, 1992, pp. 679-701. https://hrcak.srce.hr/137126. Accessed 21 Apr. 2021.
Chicago 17th Edition
Servis, Kenneth L., Edward V. Koh and Peter Baine. "Deuterium Isotope Effects on the Carbon-13 Chemical Shifts in 2-Substituted-2-Norbornyl Cations." Croatica Chemica Acta 65, no. 3 (1992): 679-701. https://hrcak.srce.hr/137126
Harvard
Servis, K.L., Koh, E.V., and Baine, P. (1992). 'Deuterium Isotope Effects on the Carbon-13 Chemical Shifts in 2-Substituted-2-Norbornyl Cations', Croatica Chemica Acta, 65(3), pp. 679-701. Available at: https://hrcak.srce.hr/137126 (Accessed 21 April 2021)
Vancouver
Servis KL, Koh EV, Baine P. Deuterium Isotope Effects on the Carbon-13 Chemical Shifts in 2-Substituted-2-Norbornyl Cations. Croatica Chemica Acta [Internet]. 1992 [cited 2021 April 21];65(3):679-701. Available from: https://hrcak.srce.hr/137126
IEEE
K.L. Servis, E.V. Koh and P. Baine, "Deuterium Isotope Effects on the Carbon-13 Chemical Shifts in 2-Substituted-2-Norbornyl Cations", Croatica Chemica Acta, vol.65, no. 3, pp. 679-701, 1992. [Online]. Available: https://hrcak.srce.hr/137126. [Accessed: 21 April 2021]

Abstracts
Deuterium isotope effects on carbon-13 chemical shifts have been determined for 2-methyl-2-norbornyl-2-dj cation, 2-methyl -2-norbornyl-exo -G-<21 cation, 2-methyl-2-norbornyl-encfo-G-di cation, 2-methyl-2-n orbo rnyl-exo,ero- 5,6-d2 cation, 2-methyl-2-norbornyl-exo, anli-6,7-đ2 cation, 2-aryl-2-norbor- nyl-1 -dj cation, 2-aryl-2-norbornyl-exo-G-cf1 cation, 2-aryl-2-norbornyI-enđo-6- di cation, 2-aiyl-2-norbornyl-exo,exo-5,6-cf2 cation, and 2-aryl-2-norbomyl- exo,anti-G,l-d2 cation. The deuterium isotope effects exhibit different magnitudes for the different isotopomers. For the 2-methyl-2-norbornyl cation, the isotope effect at C2 is 1.4 ppm for exo-G-dlt 0.9 ppm for endo-G-d^, and 0.1 ppm for 1-dj. Large positive 3-bond isotope effects are highly unusual but are consistent with the bridged structure for this ion. The isotope effects, AC(D), at the cation center have been plotted vs. oc+ constants for each of the deuterated 2-aryl-2-norbornyl cation series and compared to plots of the isotope effects, AC(D), vs. I3C chemical shifts at the cation center. The nonlinear behavior of these plots is consistent with the onset of bridging. The onset of delocalization in the 2-aryl-2-norbornyl cation as a result of electron withdrawing groups on the phenyl ring gives enhanced positive values for the isotope shifts at C2 for deuterium substitution at Cg and reduced positive values for deuterium substitution at Cj. Isotopic substitution appears to readily perturb the vibrational averaging occurring in the relatively flat an- harmonic potential well for these systems as the electron demand increases.

Hrčak ID: 137126

URI
https://hrcak.srce.hr/137126

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