Aluminum complexes, specifically those employing bulky ligand frameworks such as sal (sal = 2-[CH═N(2,6-iPr2-C6H3)]-4,6-tBu2-phenoxide) and alpha-diimine (alpha-diimine = [(2,6-iPr2-C6H3)N═C(Me)]2) derivatives are studied in various contexts. During ethylene polymerization with LCu(II) catalysts in the presence of methylaluminoxane (MAO), ligand (L) transfer is observed from the copper centre to the aluminum centre present in MAO. In the alpha-diimine case, an (imino-amido)AlMe2 complex is formed by alpha-diimine ligand transfer to aluminum followed by alkylation of one imino moiety in the ligand backbone. These ligand transfer products are then shown to be active as ethylene polymerization catalysts, bringing into question the role of the copper species.
The (sal)AlMe2, (sal)AlMeCl and (imino-amido)AlMe2 complexes were also used as initiators in the ring-opening polymerization of epsilon-caprolactone. Polymerization was studied with and without addition of tert-butanol as a co-initiator to determine its role and necessity in the catalytic cycle.
Finally, the (imino-amido)AlMe2 complex was also used as the starting complex in attempts at forming a mononuclear aluminum(I) target species. Reaction of (imino-amido)AlMe2 with excess I2 proved successful in forming the isolable precursor, (imino-amido)AlI2. Attempts at reducing (imino-amido)AlI2 with excess potassium were carried out in hopes of forming a very rare example of a mononuclear aluminum(I) species.
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:SSU.etd-05272009-142704 |
| Date | 10 June 2009 |
| Creators | Olson, Jeremy Alan |
| Contributors | Foley, Stephen R. |
| Publisher | University of Saskatchewan |
| Source Sets | Library and Archives Canada ETDs Repository / Centre d'archives des thèses électroniques de Bibliothèque et Archives Canada |
| Language | English |
| Detected Language | English |
| Type | text |
| Format | application/pdf |
| Source | http://library.usask.ca/theses/available/etd-05272009-142704/ |
| Rights | unrestricted, I hereby certify that, if appropriate, I have obtained and attached hereto a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted is the same as that approved by my advisory committee. I hereby grant to University of Saskatchewan or its agents the non-exclusive license to archive and make accessible, under the conditions specified below, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report. |
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