Show simple item record

dc.contributor.authorFrederick, Fred Charlesen_US
dc.date.accessioned2014-03-14T21:18:26Z
dc.date.available2014-03-14T21:18:26Z
dc.date.issued1983-12-15en_US
dc.identifier.otheretd-08282003-155333en_US
dc.identifier.urihttp://hdl.handle.net/10919/39290
dc.description.abstractManganese(II) and (III) complexes of potentially bidentate and tridentate Schiff base ligands have been prepared. The ligands were prepared from substituted salicylaldehyde or pyridine-2-carboxaldehyde and amines with hydrocarbon or alkylpyridyl substituents. The electrochemistry and the oxygenation kinetics of these and similar tetradentate, pentadentate, and hexadentate complexes have been studied. The electrochemistry of the majority of the complexes involves the Mn(III)/Mn(II) couple. However, varying the solvent shows that electron transfer is often accompanied by slow changes in the number of solvent molecules coordinated to the metal or changes in the actual denticity of the ligand. Activation energies and entropies for the reactions with 02 show that a large number of parameters influence the rate of reaction. Primary among these is competition between 02, solvent molecules, and donor atoms from the ligands for coordination sites on the metal. However, the reactions were all (with one exception) found to be first order in both complex and 02, implying that the slow step is formation of a Mn(III)-superoxo complex. The exception was with complexes of the tetradentate Mn(SALCn) type, where a simple rate law could not be fitted. This was explained by either steric hindrance or polymerization of the complex due to the flexibility imparted by the long polymethylene chain in the tetradentate ligand.en_US
dc.format.mediumBTDen_US
dc.publisherVirginia Techen_US
dc.relation.haspartfrederick.pdfen_US
dc.subjectManganeseen_US
dc.subjectComplex compoundsen_US
dc.subjectTransition metal compoundsen_US
dc.subject.lccLD5655.V856 1983.F743en_US
dc.titleThe effect of denticity on the electrochemistry and oxygenation kinetics of polydentate Schiff base complexes of manganeseen_US
dc.typeDissertationen_US
dc.contributor.departmentChemistryen_US
dc.description.degreePh. D.en_US
thesis.degree.namePh. D.en_US
thesis.degree.leveldoctoralen_US
thesis.degree.grantorVirginia Polytechnic Institute and State Universityen_US
thesis.degree.disciplineChemistryen_US
dc.contributor.committeechairTaylor, Larry T.en_US
dc.contributor.committeememberMason, John G.en_US
dc.contributor.committeememberHanson, Brian E.en_US
dc.contributor.committeememberFinklea, Harry O.en_US
dc.identifier.sourceurlhttp://scholar.lib.vt.edu/theses/available/etd-08282003-155333/en_US
dc.date.sdate2003-08-28en_US
dc.date.rdate2003-08-28
dc.date.adate2003-08-28en_US


Files in this item

Thumbnail

This item appears in the following Collection(s)

Show simple item record