ELECTROCHEMICAL AND SPECTROSCOPIC STUDIES OF THIOETHER COORDINATION COMPLEXES (CYCLIC VOLTAMMETRY, OCTAHEDRAL LOW-SPIN METALS, BLUE COPPER PROTEINS, ELECTRON PARAMAGNETIC RESONANCE).

Persistent Link:
http://hdl.handle.net/10150/188102
Title:
ELECTROCHEMICAL AND SPECTROSCOPIC STUDIES OF THIOETHER COORDINATION COMPLEXES (CYCLIC VOLTAMMETRY, OCTAHEDRAL LOW-SPIN METALS, BLUE COPPER PROTEINS, ELECTRON PARAMAGNETIC RESONANCE).
Author:
SWANSON, DALE DORSETT.
Issue Date:
1985
Publisher:
The University of Arizona.
Rights:
Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.
Abstract:
The bis 1,4,7-trithiacyclononane (1,4,7-TTCN) complexes of iron, cobalt, nickel and copper are reported in this work. Their properties have been examined using computer-controlled electrochemical and spectroscopic techniques. These TTCN complexes form readily, are unusually symmetrical and support electron transfer reactions at the metal center. The cobalt(II) complex is octahedral, low spin and symmetrical. Four oxidation states of cobalt-TTCN complex are observed; two one-electron transfer processes are reversible. Copper (II) bis 1,4,7-TTCN is unusually symmetrical evidenced by both solid phase and ambient temperature aqueous phase electron paramagnetic resonance spectra. An unusually high redox potential for the copper complex indicates extraordinary stability of the Cu(I) oxidation state but evidently not at the expense of Cu(II) stability. The complex also has a high formation constant compared to other copper-thioether complexes. This unusual strength of thioether donor is attributed to ligand geometry. The 1,4,7-TTCN molecule is the only known cyclic polythioether to have all sulfur atoms endodentate. This structure contributes to thermodynamic stability of complexes as the ground state configuration of the free ligand is maintained in the complex.
Type:
text; Dissertation-Reproduction (electronic)
Keywords:
Halides -- Spectra.; Halides -- Electric properties.; Sulfides -- Spectra.; Sulfides -- Electric properties.
Degree Name:
Ph.D.
Degree Level:
doctoral
Degree Program:
Chemistry; Graduate College
Degree Grantor:
University of Arizona
Advisor:
Wilson, George S.

Full metadata record

DC FieldValue Language
dc.language.isoenen_US
dc.titleELECTROCHEMICAL AND SPECTROSCOPIC STUDIES OF THIOETHER COORDINATION COMPLEXES (CYCLIC VOLTAMMETRY, OCTAHEDRAL LOW-SPIN METALS, BLUE COPPER PROTEINS, ELECTRON PARAMAGNETIC RESONANCE).en_US
dc.creatorSWANSON, DALE DORSETT.en_US
dc.contributor.authorSWANSON, DALE DORSETT.en_US
dc.date.issued1985en_US
dc.publisherThe University of Arizona.en_US
dc.rightsCopyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.en_US
dc.description.abstractThe bis 1,4,7-trithiacyclononane (1,4,7-TTCN) complexes of iron, cobalt, nickel and copper are reported in this work. Their properties have been examined using computer-controlled electrochemical and spectroscopic techniques. These TTCN complexes form readily, are unusually symmetrical and support electron transfer reactions at the metal center. The cobalt(II) complex is octahedral, low spin and symmetrical. Four oxidation states of cobalt-TTCN complex are observed; two one-electron transfer processes are reversible. Copper (II) bis 1,4,7-TTCN is unusually symmetrical evidenced by both solid phase and ambient temperature aqueous phase electron paramagnetic resonance spectra. An unusually high redox potential for the copper complex indicates extraordinary stability of the Cu(I) oxidation state but evidently not at the expense of Cu(II) stability. The complex also has a high formation constant compared to other copper-thioether complexes. This unusual strength of thioether donor is attributed to ligand geometry. The 1,4,7-TTCN molecule is the only known cyclic polythioether to have all sulfur atoms endodentate. This structure contributes to thermodynamic stability of complexes as the ground state configuration of the free ligand is maintained in the complex.en_US
dc.typetexten_US
dc.typeDissertation-Reproduction (electronic)en_US
dc.subjectHalides -- Spectra.en_US
dc.subjectHalides -- Electric properties.en_US
dc.subjectSulfides -- Spectra.en_US
dc.subjectSulfides -- Electric properties.en_US
thesis.degree.namePh.D.en_US
thesis.degree.leveldoctoralen_US
thesis.degree.disciplineChemistryen_US
thesis.degree.disciplineGraduate Collegeen_US
thesis.degree.grantorUniversity of Arizonaen_US
dc.contributor.advisorWilson, George S.en_US
dc.contributor.committeememberGlass, Richard S.en_US
dc.contributor.committeememberBurke, Michael F.en_US
dc.contributor.committeememberFernando, Quintusen_US
dc.identifier.proquest8603161en_US
dc.identifier.oclc696817544en_US
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