Development of metal-ligand cooperation in bis(phosphinimine)pyrrolide complexes of rhodium

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dc.contributor.authorMacNeil, Connor
dc.contributor.authorUniversity of Lethbridge. Faculty of Arts and Science
dc.contributor.supervisorHayes, Paul G.
dc.date.accessioned2021-09-09T16:12:07Z
dc.date.available2021-09-09T16:12:07Z
dc.date.issued2021
dc.degree.levelPh.Den_US
dc.description.abstractThe synthesis and characterization of bis(phosphinimine)pyrrolide complexes of rhodium is described. A combination of solution and solid-state spectroscopies, X-ray crystallography, and computational analyses were used to characterize relevant compounds. Crystallographic analysis of phosphinimine fragments in the reported rhodium complexes showed significant P–N bond elongation relative to uncoordinated phosphinimines in both the parent ligand scaffold and partially-coordinated (κ2-N,N) species, emphasizing the ylidic structure of the P–N linkage. In the rhodium complexes surveyed, hemilabile phosphinimines were shown to engage small molecule substrates leading to heterolytic cleavage of H2, CO deoxygenation, dehydrogenation of hydrosilanes, and the reversible activation of B–H bonds. Catalytic hydrogenation of alkenes and alkynes could be initiated from well-defined mononuclear complexes of the bis(phosphinimine)pyrrolido ligand. Taken together, the incorporation of phosphinimines in a monoanionic ligand scaffold paired with rhodium enabled new reactivities, representing an advancement in metal-ligand cooperation.en_US
dc.identifier.urihttps://hdl.handle.net/10133/6016
dc.language.isoen_USen_US
dc.proquest.subjectChemistry [0485]en_US
dc.proquest.subjectAnalytical chemistry [0486]en_US
dc.proquest.subjectMolecular chemistry [0431]en_US
dc.proquestyesYesen_US
dc.publisherLethbridge, Alta. : University of Lethbridge, Dept. of Chemistry & Biochemistryen_US
dc.publisher.departmentDepartment of Chemistry and Biochemistryen_US
dc.publisher.facultyArts and Scienceen_US
dc.relation.ispartofseriesThesis (University of Lethbridge. Faculty of Arts and Science)en_US
dc.subjectChemistryen_US
dc.subjectAnalytical chemistryen_US
dc.subjectDissertations, Academicen_US
dc.subjectMetallurgical analysisen_US
dc.subjectRhodiumen_US
dc.subjectSpectrophotometryen_US
dc.subjectX-ray crystallographyen_US
dc.titleDevelopment of metal-ligand cooperation in bis(phosphinimine)pyrrolide complexes of rhodiumen_US
dc.typeThesisen_US
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