New Haven , Connecticut 06511
نویسندگان
چکیده
The rapid, degenerate 1,2-hydride shift in 2,3-dimethyl-2-butyl cation in stable solution in SbF5/ S02C1F was perturbed by deuterium and 13C leading to splittings observed by 13C NMR spectros copy 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.
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