A variety of organic reactions provide experimental observations that are not
explained by current models of reactivity and selectivity. This dissertation describes a
combination of experimental and theoretical studies of such reactions. In the ene
reaction of singlet oxygen with tetramethylene, it is found that standard statistical rate
theories fail to account for the observed kinetic isotope effects, particularly with regard
to their broad temperature independence. Dynamics trajectories are found to account for
the observed isotope effects. In the dimerization of cyclopentadiene, novel "dynamic"
isotope effects are observed on the 13C distribution in the product, and a method for the
prediction of these isotope effects is developed here. In the cycloaddition of
diazomethane with dimethylfulvene, it is found that the current model of the mechanism
as a [6 + 4] cycloaddition is incorrect, and a new mechanism is proposed. Isotope
effects have been measured for the recently reported unusual "on water" quadricyclane
cycloadditions, and the implications of these observations toward the mechanism are
discussed.
| Identifer | oai:union.ndltd.org:tamu.edu/oai:repository.tamu.edu:1969.1/ETD-TAMU-2009-05-607 |
| Date | 2009 May 1900 |
| Creators | Kelly, Kelmara K. |
| Contributors | Singleton, Daniel A. |
| Source Sets | Texas A and M University |
| Language | English |
| Detected Language | English |
| Type | Book, Thesis, Electronic Dissertation, text |
| Format | application/pdf |
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