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Spectroscopic studies of Metal(II) complexes and application of the Ni(II) complexes to olefin oligomerisation catalysis
Complexes of some divalent first row transition metal ions with various ligands have been prepared. These included bis-complexes of β-ketoenolate ligands, nickel complexes of trialkylphosphine and nickel complexes containing phosphine and β-ketoenolate ligands, and finally, tris, bis and mono(ethyle...
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| Format: | Thesis |
| Language: | English |
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Department of Chemistry
2016
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| _version_ | 1867614154915840000 |
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| access_status_str | Open Access |
| author | Bennett, Alison Margaret Anne |
| author2 | Thornton, David A |
| author_browse | Bennett, Alison Margaret Anne Thornton, David A |
| author_facet | Thornton, David A Bennett, Alison Margaret Anne |
| author_sort | Bennett, Alison Margaret Anne |
| collection | Thesis |
| description | Complexes of some divalent first row transition metal ions with various ligands have been prepared. These included bis-complexes of β-ketoenolate ligands, nickel complexes of trialkylphosphine and nickel complexes containing phosphine and β-ketoenolate ligands, and finally, tris, bis and mono(ethylenediamine) complexes. Composition was ascertained by microanalysis and ¹H, ¹³C NMR of the diamagnetic complexes. In addition, the crystal structure of one of the nickel β-ketoenolate triethylphosphine complexes was determined. The infrared spectra of the above compounds have been examined over the range 4000-50 cm⁻¹ with a view to determining band assignments based on metal ion substitution, ligand substitution (for phosphine and β-ketoenolate complexes), ligand and metal ion isotopic labelling [for tris(ethylenediamine) complexes] and anion substitution (for phosphine and ethylenediamine complexes). In each case, spectra-structure correlations have been established and are discussed. Each of the nickel complexes prepared above was tested as a catalyst for the oligomerisation of 1-hexene. The experiments were carried out in batch at 40°C using toluene as solvent. Four different Lewis acid cocatalysts were tested and nickel : co-catalyst ratios of 1:1 and 1:10 were used. The effects of Lewis acid strength and concentration, nickel complex structure, a change in the donor chelating atom and the presence of phosphine ligands on the isomerisation, as well as the activity and selectivity of the oligomerisation reaction, are discussed. Two polymer-supported catalyst complexes have been prepared; the first,: by polymerisation of a nickel β-ketoenolate complex monomer and th, second, by binding a nickel β-ketoenolate phosphine complex to a polystyrene support through the phosphine ligand. The resultinJ polymers were extensively characterised by microanalysis, infrared, ¹H and ¹³C NMR, mass spectrometry, energy dispersive X-ray and thermal techniques. In the presence of a ten-fold excess of the ethylaluminium dichloride co-catalyst, each supported complex formed an active 1-hexene oligomerisation and isomerisation system. The activity and selectivity of each system have been compared to that of their respective monomers. Finally, the polymerised ,8-ketoenolate monomer was tested at various temperatures as a propene oligomerisation catalyst and the effect of temperature on activity and selectivity is discussed. |
| format | Thesis |
| id | oai:open.uct.ac.za:11427/22505 |
| institution | University of Cape Town (South Africa) |
| language | eng |
| last_indexed | 2026-06-10T12:47:32.500Z |
| license_str | Not specified — see source repository |
| provenance_str_mv | Harvested via OAI-PMH from UCTD — University of Cape Town Open Access Repository |
| publishDate | 2016 |
| publishDateRange | 2016 |
| publishDateSort | 2016 |
| publisher | Department of Chemistry |
| publisherStr | Department of Chemistry |
| record_format | dspace |
| source_str | UCTD — University of Cape Town Open Access Repository |
| spelling | oai:open.uct.ac.za:11427/22505 Spectroscopic studies of Metal(II) complexes and application of the Ni(II) complexes to olefin oligomerisation catalysis Bennett, Alison Margaret Anne Thornton, David A Foulds, Gary André Chemistry Complexes of some divalent first row transition metal ions with various ligands have been prepared. These included bis-complexes of β-ketoenolate ligands, nickel complexes of trialkylphosphine and nickel complexes containing phosphine and β-ketoenolate ligands, and finally, tris, bis and mono(ethylenediamine) complexes. Composition was ascertained by microanalysis and ¹H, ¹³C NMR of the diamagnetic complexes. In addition, the crystal structure of one of the nickel β-ketoenolate triethylphosphine complexes was determined. The infrared spectra of the above compounds have been examined over the range 4000-50 cm⁻¹ with a view to determining band assignments based on metal ion substitution, ligand substitution (for phosphine and β-ketoenolate complexes), ligand and metal ion isotopic labelling [for tris(ethylenediamine) complexes] and anion substitution (for phosphine and ethylenediamine complexes). In each case, spectra-structure correlations have been established and are discussed. Each of the nickel complexes prepared above was tested as a catalyst for the oligomerisation of 1-hexene. The experiments were carried out in batch at 40°C using toluene as solvent. Four different Lewis acid cocatalysts were tested and nickel : co-catalyst ratios of 1:1 and 1:10 were used. The effects of Lewis acid strength and concentration, nickel complex structure, a change in the donor chelating atom and the presence of phosphine ligands on the isomerisation, as well as the activity and selectivity of the oligomerisation reaction, are discussed. Two polymer-supported catalyst complexes have been prepared; the first,: by polymerisation of a nickel β-ketoenolate complex monomer and th, second, by binding a nickel β-ketoenolate phosphine complex to a polystyrene support through the phosphine ligand. The resultinJ polymers were extensively characterised by microanalysis, infrared, ¹H and ¹³C NMR, mass spectrometry, energy dispersive X-ray and thermal techniques. In the presence of a ten-fold excess of the ethylaluminium dichloride co-catalyst, each supported complex formed an active 1-hexene oligomerisation and isomerisation system. The activity and selectivity of each system have been compared to that of their respective monomers. Finally, the polymerised ,8-ketoenolate monomer was tested at various temperatures as a propene oligomerisation catalyst and the effect of temperature on activity and selectivity is discussed. 2016-11-10T14:17:08Z 2016-11-10T14:17:08Z 1990 Doctoral Thesis Doctoral PhD http://hdl.handle.net/11427/22505 eng application/pdf Department of Chemistry Faculty of Science University of Cape Town |
| spellingShingle | Chemistry Bennett, Alison Margaret Anne Spectroscopic studies of Metal(II) complexes and application of the Ni(II) complexes to olefin oligomerisation catalysis |
| thesis_degree_str | Doctoral |
| title | Spectroscopic studies of Metal(II) complexes and application of the Ni(II) complexes to olefin oligomerisation catalysis |
| title_full | Spectroscopic studies of Metal(II) complexes and application of the Ni(II) complexes to olefin oligomerisation catalysis |
| title_fullStr | Spectroscopic studies of Metal(II) complexes and application of the Ni(II) complexes to olefin oligomerisation catalysis |
| title_full_unstemmed | Spectroscopic studies of Metal(II) complexes and application of the Ni(II) complexes to olefin oligomerisation catalysis |
| title_short | Spectroscopic studies of Metal(II) complexes and application of the Ni(II) complexes to olefin oligomerisation catalysis |
| title_sort | spectroscopic studies of metal ii complexes and application of the ni ii complexes to olefin oligomerisation catalysis |
| topic | Chemistry |
| url | http://hdl.handle.net/11427/22505 |
| work_keys_str_mv | AT bennettalisonmargaretanne spectroscopicstudiesofmetaliicomplexesandapplicationoftheniiicomplexestoolefinoligomerisationcatalysis |