by Yiu-bong Leung. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1994. / Includes bibliographical references (leaves 67-68). / Abstract --- p.i / Acknowledgment --- p.ii / Abbreviation --- p.iii / List of spectra --- p.iv / Contents --- p.v / Chapter Part 1: --- A New Synthesis of Rhodium(II) and Iridium(II) Octaethyl- porphyrin Dimers / Chapter 1.1 --- Introduction / Chapter 1.1.1 --- Objective --- p.1 / Chapter 1.1.2 --- Literature Survey --- p.1-7 / Chapter 1.2 --- Result and Discussion --- p.8-10 / Chapter 1.3 --- Conclusion --- p.11 / Chapter Part 2: --- Substituent Effect of meso-pαrα-Arylsubstituted Octabromo- tetraphenylporphyrins / Chapter 2.1 --- Introduction / Chapter 2.1.1 --- Objective --- p.12 / Chapter 2.1.2 --- Literature Survey --- p.12-17 / Chapter 2.2 --- Result and Discussion --- p.18-28 / Chapter 2.3 --- Conclusion --- p.29 / Chapter Part 3: --- "Thermolysis of [2，3，7，8,12,13,17,18-0ctachloro-5,10,15,20- tetrakis(4'-tert-butylphenyl)porphyrinato]-2-phenylethyl- rhodium(III)" / Chapter 3.1 --- Introduction / Chapter 3.1.1 --- Objective --- p.30 / Chapter 3.1.2 --- Literature Survey --- p.30-31 / Chapter 3.2 --- Result and Discussion --- p.32-45 / Chapter 3.3 --- Conclusion --- p.46 / Experimental Section --- p.47-64 / References --- p.65-68 / Spectra --- p.69-83

Thesis (Ph. D.)--University of Missouri-Columbia, 2001. / Typescript. Vita. Includes bibliographical references (leaves 123-128). Also available on the Internet.

Thesis (Ph. D.)--University of Missouri-Columbia, 2001. / Typescript. Vita. Includes bibliographical references (leaves 123-128). Also available on the Internet.

abstract / Biological Sciences / Doctoral / Doctor of Philosophy

Using computational methods, we have investigated the chemistry of 3-phenylpropyl radical systems. These systems are of importance to polymer chemistry as free radical additions involving these species are integral in the production of styrene-containing plastics. Although the addition reactions have been well studied, the other reaction pathways, namely f3-fragmentation and cyclization, have not been as comprehensively studied. As a result, our computational study involved 3-phenylpropyl radical systems that had been systematically mono-substituted at five positions, two on the propyl chain and three on the aromatic ring. This computational analysis consisted of calculation of optimized geometries and energies for reactants, products, and transition states, followed by examination of derived thermochemical quantities (enthalpies of activation and reaction), and critical structural parameters (transition bond lengths and bond angles) of the systems. Finally correlation of structure and reactivity of the various systems was attempted. Density functional theory (DFT) using the B3-LYP functional and the 6-31 G(d) basis set was selected as the level of theory. / Department of Chemistry

Diels-Alder [4+2] cycloaddition of a mixture of 1- and 2 methylcyclopentadiene to 2-phenyl-g.-benzoquinone affords a mixture of four nd cycloadducts. A single, isomerically pure cycloadduct was isolated by careful column chromatography. Stereospecific reduction of this material with sodium borohydride and cerium(III) chloride 'affords a single, isomerically pure tricyclic diol. The structures of the cycloadduct and this tricyclic diol, established via analysis of their one- and two-dimensionial NMR spectra, were shown to be (1-methyl-5-phenyltricyclo[6.2.1.02,7]undec a-4,9 diene-3,6-dione and 1-methyl-5-phenyltricyclo[6.2.1.0 2 ,7 ]undeca-4,9-diene t.&A-3-=.a-6-diol), respectively. Intramolecular [2+2] photocyclization of this tricyclic diol afforded the corresponding cage diol, 3-methyl-7phenylpentacyclo[5.4.0.0 2 ,6 .03 , 1 0 .05, 9 ]undecane-.exogxa-8,11-diol. Oxidation of this cage diol with pyridinium chlorochromate in dry dichloromethane afforded a single, isomerically pure cage hydroxyketone, 3-methyl-7 phenylpentacyclo[5.4.02,6.03,l .1519]undecane-xA-8-ol-II-one, whose structure was established by single crystal X-ray crystallographic methods.

The purpose of this work was to investigate the reaction of allena and phenyl azide, in order to gain greater insight into the reaction of aryl azides with allenes.