University of SaskatchewaneCommons
  • Browse
    • All of eCommons
    • Communities & Collections
    • By Issue Date
    • Authors
    • Titles
    • Subjects
    • This Collection
    • By Issue Date
    • Authors
    • Titles
    • Subjects
  • My Account
    • Login
    • Register
        • Login
        View Item 
        • eCommons Home
        • College of Graduate and Postdoctoral Studies
        • Electronic Theses and Dissertations
        • View Item
        • eCommons Home
        • College of Graduate and Postdoctoral Studies
        • Electronic Theses and Dissertations
        • View Item
        JavaScript is disabled for your browser. Some features of this site may not work without it.

        Synthesis of £^-Diimine and iminoisoindoline ligands for applications in palladium and aluminum coordination chemistry and catalysis

        Thumbnail
        View/Open
        JacksonMChitandaPhDThesis.pdf (2.491Mb)
        Date
        2009-11
        Author
        Chitanda, Jackson Mulenga
        Type
        Thesis
        Degree Level
        Doctoral
        Abstract
        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 di-ortho-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(ƒÝ-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(ƒÝ-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. 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. 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{ƒÝ-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, p-acetylbromobenzene and p-chlorobenzaldehyde, respectively in the Heck coupling reaction.
        Degree
        Doctor of Philosophy (Ph.D.)
        Department
        Chemistry
        Program
        Chemistry
        Supervisor
        Foley, Stephen R.
        Copyright Date
        November 2009
        URI
        http://hdl.handle.net/10388/etd-12092009-153342
        Subject
        Palladium
        £^-Diimine
        Coordination Chemistry and Catalysis
        Iminoisoindoline
        Aluminum
        Collections
        • Electronic Theses and Dissertations
        • College of Graduate Studies & Research
        • University Library
        University of Saskatchewan

        © University of Saskatchewan
        Contact Us | Disclaimer | Privacy