This work began with the synthesis and full characterization of a novel £^-diimine ligand, (2,6-iPr2C6H3N=CH)2C6H4, from the reaction of o-phthaladehyde and the bulky aniline, 2,6-diisopropylaniline. It was observed that any <i>di-ortho</i>-substituted aniline with less bulky groups than isopropyl groups resulted in formation of the corresponding iminisoindolines. Reaction of the £^-diimine ligand with PdCl2 did not result in a seven-membered coordination complex, but in non-palladacyclic complex, [(g-diimine)PdCl(Ý-Cl)]2. Whereas reaction with Pd(OAc)2 gave an S-shaped five-membered trinuclear palladacyclic complex, {1,2-(2,6-iPr2-C6H3N=CH)2-C6H3]Pd(Ý-OAc)2}2Pd. These complexes were found to be active precatalysts for Heck and Suzuki coupling reaction giving TONs of up to 104 and 86, for arylbromides and arylchlorides, respectively.<p>
On the other hand, a series of neutral and cationic seven-membered aluminum coordination complexes were obtained from the reaction of £^-diimine with a variety of aluminum species (AlMe3, AlMe2Cl, AlMeCl2 and AlCl3). The synthesis and characterization of these complexes are exemplified.<p>
Also illustrated in this thesis is the synthesis and characterization of a series of air- and moisture-stable iminoisoindoline-based palladacyclic compounds of the general formula, [(iminoisoindoline)Pd{Ý-OAc}]2. These six-membered palladacyclic complexes were obtained through a simple two-step protocol as analytically pure solids. Phosphine-ligated mononuclear palladacycles of the general formula, [Pd(iminoisoindoline)X(PR3)], X= OAc or Cl, R = Ph or Cy, are also described. Dinuclear palladacycles were also found to be active for the Heck and Suzuki C-C coupling reactions. TONs of up to 106, 105 and 60 were observed for coupling of iodobenzene, <i>p</i>-acetylbromobenzene and <i>p</i>-chlorobenzaldehyde, respectively in the Heck coupling reaction.
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:SSU.etd-12092009-153342 |
| Date | 10 December 2009 |
| Creators | Chitanda, Jackson Mulenga |
| 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-12092009-153342/ |
| Rights | restricted, 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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