Syntheses and applications of group VI and VIII-X heterocyclic-phosphinimine complexes.
Date of Award
Chemistry and Biochemistry
Stephan, Douglas W.,
Creative Commons License
This work is licensed under a Creative Commons Attribution-Noncommercial-No Derivative Works 4.0 License.
A class of phosphinimine-based group VI and VIII-X late transition metal (LTM) complexes has been synthesized and evaluated for olefin polymerisation activity. The phosphinimine ligand has been designed to incorporate an imine moiety; a functional group which has been successfully applied in very active LTM olefin catalytic systems. Heterocycles, such as pyridine and imidazole are used to accomplish the integration of an imine group into the ligand. Phosphines employing the heterocyclic group are oxidized by phenyl azides in excellent yields to form phosphinimine ligands. These phosphinimine ligands react with several LTM's, the complexes of which are identified by single crystal diffraction studies, elemental analysis, NMR and IR spectroscopy, and magnetic susceptibility measurements. In contrast to highly active imine-based systems, we find iron(II) and nickel(II) complexes with bulky phosphinimine-based ligands oligomerise ethylene to form C4 alkenes with moderate activities. (Abstract shortened by UMI.)Dept. of Chemistry and Biochemistry. Paper copy at Leddy Library: Theses & Major Papers - Basement, West Bldg. / Call Number: Thesis2002 .S67. Source: Masters Abstracts International, Volume: 43-01, page: 0217. Adviser: Douglas W. Stephan. Thesis (M.Sc.)--University of Windsor (Canada), 2003.
Spencer, Liam P., "Syntheses and applications of group VI and VIII-X heterocyclic-phosphinimine complexes." (2003). Electronic Theses and Dissertations. 3685.