The reactions of the ethyl radical with a series of allyl compounds were examined experimentally in the gas phase, and the results were seen to conform to a general mechanism. Specifically, the ethyl radical can abstract a hydrogen atom from the allyl compound, or add to the olefinic linkage of the allyl compound. Dismutation reactions of the product radicals formed in the addition or abstraction reactions were also observed in this study. The metathesis reactions of some allyl compounds were too slow to be measured unless the functional group was deuterated. When this was done in the case of allyl alcohol and allyl formate, primary isotope effects in metathesis could be measured, and were in good agreement with the values predicted on the basis of zero point energy differences. The activation energies of the dismutation reactions of the adduct radicals ranged from 15 to 27 Kcal/mole and were found to depend on the estimated enthalpies of this reaction. In certain cases, a choice between two different reaction routes of the dismutation reaction could be made by comparing the activation energy with the estimated enthalpy change. The dismutation reaction offers a convenient method for the generation of free radicals at low temperatures. In this way, the allyl and ethoxy radicals were generated, and their disproportionation-combination ratios with the ethyl radical were measured. The kinetics of interaction of the ethyl radical with an allyl compound in the gas phase can be compared with the polymerization of that monomer in the liquid phase. Specifically the ratio of the addition rate constant to the metathesis rate constant in the gas phase can be related to the degree of polymerization and a linear relationship between these quantities was found in this study. / Science, Faculty of / Chemistry, Department of / Graduate

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Diss. (sammanfattning) Uppsala : Univ, 2001. / Härtill 4 uppsatser.

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Thesis (Ph. D.)--University of Chicago, Department of Chemistry, December 2003. / Includes bibliographical references. Also available on the Internet.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1959. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 88-89).

To gain better understanding of the nature of the carbonmetal bonding in 3-neopentylallyl alkali metal (5,5-dimethyl- 2-hexenyl alkali metal) systems, an investigation is extended to 3-neopentylallylpotassium. In addition, pertinent data on the 3-neopentylallyl systems are re-examined in an attempt to understand the trends in the bonding habits, as affected by the solvent, the cation and the temperature.