Rearrangements of Radical Anions Generated from Cyclopropyl Ketones

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dc.contributor.authorPhillips, Janice Paigeen
dc.contributor.committeechairTanko, James M.en
dc.contributor.committeememberAnderson, Mark R.en
dc.contributor.committeememberCastagnoli, Neal Jr.en
dc.contributor.committeememberBrewer, Karen J.en
dc.contributor.committeememberWolfe, James F.en
dc.contributor.committeememberGibson, Harry W.en
dc.contributor.departmentChemistryen
dc.date.accessioned2014-03-14T21:22:15Zen
dc.date.adate1998-11-11en
dc.date.available2014-03-14T21:22:15Zen
dc.date.issued1998-05-04en
dc.date.rdate1999-11-11en
dc.date.sdate1998-10-25en
dc.description.abstractCyclopropyl-containing substrates have been frequently utilized as "probes" for the detection of SET pathways in organic and biorganic systems. These reactions are based on the cyclorpropylcarbinyl → homoallyl rearrangement, which is fast and essentially irreversible. The implicit assumption in such studies is that if a "radical" species is produced, it will undergo ring opening. We have found that there are two important factors to consider in the design of SET probes: 1) ring strain, the thermodynamic driving force for the rearrangement, and 2) resonance energy, which may help or hinder rearrangement, depending on the specific system. Delocalization of spin and charge were found to be important factors pertaining to substituent effects on the rates of radical anion rearrangements. Previous studies from our lab have centered on highly conjugated phenyl cyclopropyl ketones. This work considers a series of compounds varying in their conjugative components from a highly conjugated spiro[2.5]octa-4,7-dien-6-one and derivatives to simple aliphatic ketones. Utilizing cyclic, linear sweep voltammetry, and preparative electrolysis techniques, it was discovered that all substrates yielded ring opened products with rates and selectivities that will prove useful and informative in the design of mechanistic probes based on the cyclorpropylcarbinyl → homoallyl rearrangement. Rates of homogeneous electron transfer from a series of hydrocarbon mediators to substrates were measured using homogeneous catalysis techniques. Standard reduction potentials and reorganization energies of substrates were derived using Marcus theory. Conjugative interactions with the cyclopropyl group are discussed.en
dc.description.degreePh. D.en
dc.identifier.otheretd-102498-111245en
dc.identifier.sourceurlhttp://scholar.lib.vt.edu/theses/available/etd-102498-111245/en
dc.identifier.urihttp://hdl.handle.net/10919/40178en
dc.publisherVirginia Techen
dc.relation.haspartPHILLIPS1998.PDFen
dc.rightsIn Copyrighten
dc.rights.urihttp://rightsstatements.org/vocab/InC/1.0/en
dc.subjectMarcus theoryen
dc.subjectHomogeneous catalysisen
dc.subjectReaction mechanism and kineticsen
dc.subjectCyclopropyl ketonesen
dc.subjectVoltammetryen
dc.subjectCathodic reductionen
dc.subjectRing openingen
dc.subjectRadical anionen
dc.titleRearrangements of Radical Anions Generated from Cyclopropyl Ketonesen
dc.typeDissertationen
thesis.degree.disciplineChemistryen
thesis.degree.grantorVirginia Polytechnic Institute and State Universityen
thesis.degree.leveldoctoralen
thesis.degree.namePh. D.en

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