UBC Theses and Dissertations
The synthesis of group 3 and group 4 metal amidate chloride complexes and titanium catalysts for olefin hydroamination Beard, James David
The work presented in this thesis bridges the boundaries between what is considered traditional inorganic and organic chemistry. The uniting principle is a focus on synthesis. This manifests in the development of new synthetic strategies for preparing novel organometallic complexes, and in the investigation of the reactivity of these coordination compounds. The ultimate goal is the development of rationally designed, and well characterized metal complexes for use in new catalytic organic transformations. Two routes for the synthesis of amidate complexes from group 4 metal chlorides were developed. A variety of group 4 metal bis(amidate) dichloride complexes were synthesized and characterized. The structures of three titanium bis(amidate) dichlorides complexes were solved by X-ray crystallography. The first known homoleptic yttrium amidate complex was prepared and its structure was solved by X-ray crystallography. Investigations were made into the application of titanium bis(amidate) bis(amido) complexes for the synthesis of N-heterocyclic compounds. Several titanium catalysts for the intramolecular hydroamination of unactivated alkenes were discovered. A study was undertaken to elucidate the influence that steric and electronic factors in the amidate auxiliary ligand have on the activity of titanium bis(amidate) imido hydroamination catalysts. Finally, preliminary work was done on exploring the application of lanthanide chloride complexes toward new carbon-carbon bond forming reactions, and in the development of chiral amidate ligands for potential applications in asymmetric catalysis.
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