Date of Award

12-2000

Degree Name

Master of Arts

Department

Chemistry

First Advisor

Dr. John E. Chateauneuf

Second Advisor

Dr. John B. Miller

Third Advisor

Dr. Marc W. Perkovic

Access Setting

Masters Thesis-Open Access

Abstract

Recent research interest on supercritical CO2 includes the following three important issues: 1) the development of supercritical CO2 as an environmental benign reaction medium and as a viable alternative to hazardous organic solvents, 2) the use of supercritical CO2 as a C1 feedstock for fixation of CO2 and 3) characterization of photoinduced electron transfer reactions under supercritical conditions.

The reductive photocarboxylation of aromatic hydrocarbons such as anthracene and phenanthrene in supercritical CO2, have been chosen for study. Supercritical CO2 was utilized as both a replacement solvent and as a reacting reagent for the formation of carbon-carbon bonds and addition of a functional group. By comparison with similar reactions in regular organic solvents, photocarboxylation in supercritical CO2 has higher yield and selectivity. This fundamental study helped to understand the influence of supercritical CO2 as a solvent and its influence on photocarboxylation reactions. The mechanistic investigation combined with time-resolved laser flash photolysis and other spectroscopic methods, shows that carboanion radical intermediates are involved in this photoinduced electron transfer process.

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