Calculationof Equilibrium Isotope Effects in a Conformationally Mobile Carbocation
Open Access
- 1 May 1989
- journal article
- Published by Walter de Gruyter GmbH in Zeitschrift für Naturforschung A
- Vol. 44 (5) , 480-484
- https://doi.org/10.1515/zna-1989-0518
Abstract
The rapid, degenerate 1,2-hydride shift in 2,3-dimethyl-2-butyl cation in stable solution in SbF5/SO2C1F was perturbed by deuterium and 13C leading to splittings observed by 13C NMR spectroscopy over a range of temperatures. Accurate values for equilibrium isotope effects were obtained from these data. Theoretical calculations of the equilibrium isotope effects were performed using the Gaussian-86 program to obtain an optimized geometry and the Cartesian force constant matrix, followed by the program QUIVER which applies the Bigeleisen-Mayer method. When all of the conformers, which are in rapid equilibrium, were considered specifically, quite good agreement between theory and experiment was obtained.Keywords
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