Persistent Link:
http://hdl.handle.net/10150/294029
Title:
Synthesis and Characterization of [FeFe] Hydrogenase Mimics
Author:
Swenson, Matthew
Issue Date:
2013
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.
Embargo:
Release after 10-Nov-2013
Abstract:
The hydrogenase enzyme catalytically converts protons to hydrogen. The hydrogenase enzyme contains a number of [Fe₄S₄] clusters that act as an electron transport chain, shuttling electrons to the active site. To replicate this, [FeFe]hydrogenase mimics featuring redox active quinone moieties annealed onto an Fe₂S₂(CO)₆ core were synthesized. EPR of these compounds revealed significant communication between the quinone ligand and the Fe₂S₂(CO)₆ core upon one electron reduction. Mimics featuring the redox active 2-phenylazopyridine ligand annealed onto [μ-1,3-propanedithiolato]bis(tricarbonyliron) and [μ-1,2-benzenedithiolato]bis (tricarbonyliron) were also synthesized. UV-Visible spectroscopy showed that metal to ligand charge transfer was occurring in these complexes The hydrogenase enzyme also contains a proton transport chain. [μ-1,2-Benzenedithiolato]bis(tricarbonyliron) complexes substituted with hydrogen donating phosphines were synthesized to mimic this. Attempts to synthesize the thiol substituted phosphine complex were unsuccessful, so protection group chemistry was employed. Electrochemistry of the resulting complexes showed an increase in catalytic current as well as a decrease in overpotential, when compared to the triphenylphosphine substituted complex. Finally, an effort to combine a redox active and hydrogen donating moiety into a single complex using substituted 2-phenylazopyradine moieties was attempted without success.
Type:
text; Electronic Thesis
Keywords:
hydrogenase; synthesis; Chemistry; catalysis
Degree Name:
M.S.
Degree Level:
masters
Degree Program:
Graduate College; Chemistry
Degree Grantor:
University of Arizona
Advisor:
Glass, Richard S.

Full metadata record

DC FieldValue Language
dc.language.isoenen_US
dc.titleSynthesis and Characterization of [FeFe] Hydrogenase Mimicsen_US
dc.creatorSwenson, Matthewen_US
dc.contributor.authorSwenson, Matthewen_US
dc.date.issued2013-
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.releaseRelease after 10-Nov-2013en_US
dc.description.abstractThe hydrogenase enzyme catalytically converts protons to hydrogen. The hydrogenase enzyme contains a number of [Fe₄S₄] clusters that act as an electron transport chain, shuttling electrons to the active site. To replicate this, [FeFe]hydrogenase mimics featuring redox active quinone moieties annealed onto an Fe₂S₂(CO)₆ core were synthesized. EPR of these compounds revealed significant communication between the quinone ligand and the Fe₂S₂(CO)₆ core upon one electron reduction. Mimics featuring the redox active 2-phenylazopyridine ligand annealed onto [μ-1,3-propanedithiolato]bis(tricarbonyliron) and [μ-1,2-benzenedithiolato]bis (tricarbonyliron) were also synthesized. UV-Visible spectroscopy showed that metal to ligand charge transfer was occurring in these complexes The hydrogenase enzyme also contains a proton transport chain. [μ-1,2-Benzenedithiolato]bis(tricarbonyliron) complexes substituted with hydrogen donating phosphines were synthesized to mimic this. Attempts to synthesize the thiol substituted phosphine complex were unsuccessful, so protection group chemistry was employed. Electrochemistry of the resulting complexes showed an increase in catalytic current as well as a decrease in overpotential, when compared to the triphenylphosphine substituted complex. Finally, an effort to combine a redox active and hydrogen donating moiety into a single complex using substituted 2-phenylazopyradine moieties was attempted without success.en_US
dc.typetexten_US
dc.typeElectronic Thesisen_US
dc.subjecthydrogenaseen_US
dc.subjectsynthesisen_US
dc.subjectChemistryen_US
dc.subjectcatalysisen_US
thesis.degree.nameM.S.en_US
thesis.degree.levelmastersen_US
thesis.degree.disciplineGraduate Collegeen_US
thesis.degree.disciplineChemistryen_US
thesis.degree.grantorUniversity of Arizonaen_US
dc.contributor.advisorGlass, Richard S.en_US
dc.contributor.committeememberWalker, Francis A.en_US
dc.contributor.committeememberLichtenberger, Dennis L.en_US
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