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dc.contributor.advisorOnani, Martin
dc.contributor.authorVan Wyk, Shane Cedrick
dc.date.accessioned2016-04-05T13:57:13Z
dc.date.available2016-04-05T13:57:13Z
dc.date.issued2015
dc.identifier.urihttp://hdl.handle.net/11394/4873
dc.description>Magister Scientiae - MScen_US
dc.description.abstractThis thesis reports on the syntheses of new bimetallic iminopyridyl nickel(II) and palladium(II) complexes as catalyst precursors for ethylene ligomerization/polymerization. Tetrahydrophenyl-linked iminopyridyl ligands, pyridin-2-ylmethyl-{4-[(pyridin-2-ylmethylimino)-methyl]-benzylidene}-amine (L1) and (2-pyridin-2-yl-ethyl)-{4-[(2-pyridin-2-yl-ethylimino)-methyl]-benzylidene}-amine (L2) were prepared via condensation from terephthaldehyde and 2 molar equivalents of a primary pyridylamine. Alkyl-linked iminopyridyl ligands N,N'-bis-pyridin-2-ylmethylene-propane-1,3-diamine (L3), N,N'-bispyridin- 2-ylmethylene-butane-1,4-diamine (L4) and N,N'-bis-pyridin-2-ylmethylenepentane- 1,5-diamine (L5) were prepared by condensation of 2 equivalents of 2- pyridinecarboxaldehyde and a primary diamine. The ligands were obtained as either red oils or orange solids. These ligands were characterized using Fourier-transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR), mass spectrometry (MS), elemental analysis (EA), ultraviolet-visible spectrophotometry (UV-Vis) and thermal gravimetric analysis (TGA) where applicable. The tetrahydrophenyl-linked iminopyridyl ligands were subsequently used to prepare their corresponding homobimetallic palladium(II) and nickel(II) complexes. A 1:2 reaction of the ligands with PdCl2(COD), NiCl2(DME) and NiBr2(DME) gave palladium(II) and nickel(II) complexes C1-C6 in moderate to very good yields (58-94%). The palladium(II) complexes were found to be stable, but light-sensitive solids while the nickel(II) complexes were found to be stable, but light and air sensitive solids. These complexes were characterized using FTIR, NMR, EA, MS, UV-Vis and TGA. These complexes were then tested for catalytic activity of ethylene oligomerization. It was found that complexes C1 and C5 were highly active when activated by the cocatalysts methylaluminoxane (MAO) as well as ethyl aluminium dichloride (EADC). It was found that EADC gave the highest activity so the remaining catalysts (C3 and C6) were tested exclusively with EADC. All four complexes were active for ethylene oligomerization with yields of between 2.7-6.5 g, with C5 providing the highest activity and C1 the lowest. These catalysts were highly selective towards C4 oligomers with percentages ranging from 71-81%. Optimization studies were then carried out with C3 by varying the pressure and Al:Ni ratio.en_US
dc.language.isoenen_US
dc.publisherUniversity of the Western Capeen_US
dc.subjectIminopyridyl ligandsen_US
dc.subjectCatalysisen_US
dc.subjectNickelen_US
dc.subjectPalladiumen_US
dc.titleSome new bimetallic nickel and palladium complexes for catalysis applicationsen_US
dc.rights.holderUniversity of the Western Capeen_US


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