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dc.contributor.advisorPolt, Robin L.en_US
dc.contributor.authorKelly, Brian Danielen_US
dc.creatorKelly, Brian Danielen_US
dc.date.accessioned2011-12-05T21:56:11Z
dc.date.available2011-12-05T21:56:11Z
dc.date.issued2009en_US
dc.identifier.urihttp://hdl.handle.net/10150/193634
dc.description.abstractA group of ligands were designed based on a minimalist reduction of the structure of metalloproteins. It was thought that a modular design with facile synthesis could lead to a new family of privileged ligands. Towards this goal a series of tri-, tetra, and penta-dentate ligands were synthesized. The ligands had a common chiral core based on inexpensive amino acid starting materials. A modular diamine backbone was adjusted to control the size, bite angle and electronic nature of the binding pocket. The ligands were capped with Schiff base imines to provide an initial binding point for the metal and to create steric bulk at one face of the complex.The tetra-dentate ligands were shown to efficiently bind zinc(II), copper((II), nickel(II), and palladium(II). In the case of the penta-dentate ligands the series was extended to cobalt(II), manganese(II) and iron(II). The tri-dentate ligands did not form isolated metal complexes. The structures of these complexes were confirmed by NMR, ESR and X-ray crystallography. The chiral copper complexes were applied to a model asymmetric acylation reaction. The results were disappointing as the reactions showed no stereoselectivity.
dc.language.isoENen_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.titleAMINO ACID DERIVED TRANSITION METAL COMPLEXES: STRUCTURAL AND CATALYTIC STUDIES.en_US
dc.typetexten_US
dc.typeElectronic Dissertationen_US
dc.contributor.chairPolt, Robin L.en_US
dc.identifier.oclc659752049en_US
thesis.degree.grantorUniversity of Arizonaen_US
thesis.degree.leveldoctoralen_US
dc.contributor.committeememberPolt, Robin L.en_US
dc.contributor.committeememberMash, Eugene A.en_US
dc.contributor.committeememberChristie, Hamish S.en_US
dc.contributor.committeememberEnemark, Johnen_US
dc.contributor.committeememberKukolich, Stephen S.en_US
dc.identifier.proquest10418en_US
thesis.degree.disciplineChemistryen_US
thesis.degree.disciplineGraduate Collegeen_US
thesis.degree.namePh.D.en_US
refterms.dateFOA2018-08-24T18:51:03Z
html.description.abstractA group of ligands were designed based on a minimalist reduction of the structure of metalloproteins. It was thought that a modular design with facile synthesis could lead to a new family of privileged ligands. Towards this goal a series of tri-, tetra, and penta-dentate ligands were synthesized. The ligands had a common chiral core based on inexpensive amino acid starting materials. A modular diamine backbone was adjusted to control the size, bite angle and electronic nature of the binding pocket. The ligands were capped with Schiff base imines to provide an initial binding point for the metal and to create steric bulk at one face of the complex.The tetra-dentate ligands were shown to efficiently bind zinc(II), copper((II), nickel(II), and palladium(II). In the case of the penta-dentate ligands the series was extended to cobalt(II), manganese(II) and iron(II). The tri-dentate ligands did not form isolated metal complexes. The structures of these complexes were confirmed by NMR, ESR and X-ray crystallography. The chiral copper complexes were applied to a model asymmetric acylation reaction. The results were disappointing as the reactions showed no stereoselectivity.


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