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UBC Theses and Dissertations

Applications of titanium-catalyzed hydroamination towards the syntheses of electron rich materials Thompson, August


This thesis details several topics of research related to the hydroamination reaction of terminal alkynes with amines. We used an established bis(amidate)bis(amido) titanium precatalyst to synthesize novel ferrocenyl enamines, including a diferrocene dienamine compound. These products were isolated in 84-94% yield, with the imine tautomer detectable by 1H NMR spectroscopy for only one of the products; all other products produced exclusively the enamine. Investigation of the oxidation properties of the dienamine diferrocene compound revealed communication between the two different iron centers with a distance of 15 Å between them. We developed a novel bis(amide)ferrocene ligand and investigated its properties and reactions with titanium. We also characterized a highly symmetric bis(amidate)imido tetramer titanium complex with the novel ferrocene-containing ligand in the solid-state and investigated the solution-state structure. Multi-dimensional NMR spectroscopy experiments indicate that the solution-state structure is consistent with the solid-state structure. The high thermal stability of the tetramer compound is consistent with an off-cycle species and is consistent with the reduced catalytic activity of the ferrocene-containing bis(amidate) titanium species towards hydroamination when compared with an established bis(amidate)bis(amido) titanium precatalyst. To assist in our understanding of the characteristics of the products of hydroamination between aryl terminal alkynes and aryl amines, we used primarily computational tools to investigate the effects of nitrogen when incorporated into a conjugated system.

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