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      The Versatility of Aluminum Systems: Ligand Transfer Agents and Polymerization Catalysts

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      JOMScThesis.pdf (743.4Kb)
      Date
      2009
      Author
      Olson, Jeremy Alan
      Type
      Thesis
      Degree Level
      Masters
      Metadata
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      Abstract
      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.
      Degree
      Master of Science (M.Sc.)
      Department
      Chemistry
      Program
      Chemistry
      Supervisor
      Foley, Stephen R.
      Copyright Date
      2009
      URI
      http://hdl.handle.net/10388/etd-05272009-142704
      Subject
      copper
      Chemistry
      Organometallic chemistry
      polymerization
      polyethylene
      poly(caprolactone)
      aluminum
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