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dc.contributor.advisorMead, Keith T.
dc.contributor.authorClark, Wesley D.
dc.date2015
dc.date.accessioned2020-09-03T18:04:22Z
dc.date.available2020-09-03T18:04:22Z
dc.identifier.urihttps://hdl.handle.net/11668/19611
dc.description.abstractThe synthesis and characterization of the first series of tetra-NHC-Ag(I)-X cubane clusters are reported. The clusters were characterized with 1H and 13C NMR spectroscopy, ESI-TOF MS, and single crystal X-ray diffraction. Crossover experimental data were consistent with intramolecular exchange, which can be visualized by a molecular rotating type mechanism. Additionally, CCC-NHC Zr(IV) pincer type complexes were synthesized and characterized with 1H and 13C NMR spectroscopy, CHN combustion analysis, and X-ray crystallography. A large rate effect was observed based on the halogen and metal center for the hydroamination/cyclization of unactivated aminoalkenes. Zirconium based pincers provided faster reaction rates than their hafnium counterparts (Zr>Hf). Precatalysts with iodide ligands provided faster reaction rates than their bromide and chloride counterparts (I>Br>Cl). The mechanism of hydroamination for Zr(IV) CCC-NHC complexes was also investigated for bis(iodide) and bis(amido) ligand classes. A full kinetic analysis of substrate and precatalyst have been identified along with the formation of small amounts of an oxidized product. The proposed mechanism contains an imido-type intermediate whose formation depends greatly on which set of ligand class is used.
dc.publisherMississippi State University
dc.subject.othercatalysis
dc.subject.otherorganometallic
dc.titleN-heterocyclic Carbene Complexes of Ag(I) and Zr(IV): Ag(I)-Halide Cubane Type Clusters and the Mechanism of Hydroamination with CCC-NHC Pincer Complexes
dc.typeDissertation
dc.publisher.departmentDepartment of Chemistry
dc.publisher.collegeCollege of Arts & Sciences
dc.date.authorbirth1988
dc.subject.degreeDoctor of Philosophy
dc.subject.majorChemistry
dc.contributor.committeeFoster, Stephen C.
dc.contributor.committeeEmerson, Joseph
dc.contributor.committeeLewis, Edwin
dc.contributor.committeeSygula, Andrzej


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