Date of Award
Master of Science in Chemistry - (M.S.)
Chemical Engineering and Chemistry
Joel F. Liebman
Carol A. Venanzi
Thermodynamic stabilization energies are presented for a series of monosubstituted vinyl, cyclopropyl, ethynyl, and phenyl compounds. The energies are calculated using ab initio molecular orbital calculations at the 4-31G level, and also with published experimental heat of formation data. Correlation analyses are then attempted with the dual substituent parameter approach with the stabilization energies. The analyses are also attempted with a triple-parameter approach using Topsom's theoretically calculated X, F, and Ro constants. Among the findings are the facts that π-donating substituents correlate well, while π-accepting substituents do not. Indications of the relative sensitivities of hydrocarbon frameworks to substituent electrostatic and resonance effects are analyzed. Photoelectron spectroscopy and carbon-13 chemical shift data of the substituted olefinic compounds are also examined to provide further insights.
Stevenson, Tyler Arthur, "Quantitative evaluation of substituent effects on stabilization energies of strained and unsaturated molecules" (1984). Theses. 2281.