Theoretical studies of organic systems: ruthenium catalyzed [2+2] cycloadditions and fluorine-19 NMR spectra of perfluoro-octanesulfonamides

dc.contributor.advisorGoddard, J.D.
dc.contributor.authorLiu, Peng
dc.date.accessioned2021-01-26T15:14:15Z
dc.date.available2021-01-26T15:14:15Z
dc.date.copyright2006
dc.degree.departmentDepartment of Chemistry and Biochemistryen_US
dc.degree.grantorUniversity of Guelphen_US
dc.degree.nameMaster of Scienceen_US
dc.description.abstractThe effects of substituents on the alkynes on reactivities in ruthenium catalyzed [2+2] cycloadditions have been studied using density functional theory. The theoretical studies predicted the same trends as observed in experiment. Substituents may affect the reactivities due to steric repulsions, electronic effects, and intramolecular hydrogen bonds. The effects of a remote substituent on the regioselectivity of cycloadditions of 2-substituted norbornenes with alkynes have been investigated. Theory predicted the same trends as experiment and matched the experimental product ratios well. The origin of the regioselectivities is attributed to the different strengths of the [pi](C5-C6)[right arrow][pi]*(C 2-Y) or [pi](C5-C6)[right arrow][sigma]*(C 2-Y) orbital interactions in 2-substituted norbornenes. Theoretical studies of the conformations and NMR properties of linear and branched perfluoro-octanesulfonamides (PFOSA) furnished qualitative explanations of the variable temperature 19F NMR spectra. The 19 F chemical shifts predicted by the B3LYP-GIAO method are in good agreement with experiment.en_US
dc.identifier.urihttps://hdl.handle.net/10214/23996
dc.language.isoen
dc.publisherUniversity of Guelphen_US
dc.rights.licenseAll items in the Atrium are protected by copyright with all rights reserved unless otherwise indicated.
dc.subjectsubstituentsen_US
dc.subjectalkynesen_US
dc.subjectreactivitiesen_US
dc.subjectruthenium catalyzed [2+2] cycloadditionen_US
dc.subjectdensity functional theoryen_US
dc.titleTheoretical studies of organic systems: ruthenium catalyzed [2+2] cycloadditions and fluorine-19 NMR spectra of perfluoro-octanesulfonamidesen_US
dc.typeThesisen_US

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