ORGN 468 |
| Our group has recently described a new form of kinetic isotope effect that arises from dynamic selectivity in the bifurcation of a reaction pathway on the slope of an energy surface. Since the selection between products does not occur at a potential energy saddle point, we proposed that the isotope effect is decided by dynamic factors that are not necessarily related to zero point energy effects on the surface. As an alternative explanation, it has recently been suggested that variational transition state theory can account for these isotope effects. The dynamic explanation and variational transition state theory explanation make distinct predictions as to the temperature dependence of these isotope effects. We describe here our studies of the temperature dependence of the intramolecular isotope effects for the reaction of singlet oxygen with gem-tetramethylethylene-d6. These results are used to evaluate the competing theories for the origin of the isotope effects. |
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New Reactions, Methodology, Total Synthesis, Physical Organic Chemistry
8:00 PM-10:00 PM, Tuesday, 15 March 2005 Convention Center -- Sails Pavilion, Poster
Division of Organic Chemistry |