Design, synthesis and characterization of water soluble heterobimetallic complexes and their evaluation as aqueous biphasic hydroformylation catalysts

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dc.contributor.advisorSmith, Gregory Sen_ZA
dc.contributor.advisorMakhubela, Banothile C Een_ZA
dc.contributor.authorSiangwata, Shepherden_ZA
dc.date.accessioned2016-02-05T07:26:15Z
dc.date.available2016-02-05T07:26:15Z
dc.date.issued2015en_ZA
dc.descriptionIncludes bibliographical referencesen_ZA
dc.description.abstractA series of new water-soluble N,O-chelating Schiff base ligands were synthesised. These ligands were reacted with ferrocenecarboxaldehyde through Schiff base condensation reactions, leading to new water-soluble ferrocenylimine mononuclear complexes. The mononuclear complexes were reacted with a dimeric rhodium precursor [RhCl(COD)]2 to produce a series of novel ferrocenylimine-Rh(I) heterobimetallic complexes. Both themononuclear and heterobimetallic complexes were found to have good solubility in water of up to 11 mg/mL. The complexes were characterised fully using various spectroscopic and analytical techniques including 1H NMR, 13C NMR spectroscopy, FT-IR spectroscopy, mass spectrometry and elemental analysis. In addition, mononuclear and heterobimetallic complexes were also synthesised as precursors to dendritic DAB-G1 structures. These were found to be water-soluble and they were also characterised using spectroscopic and analytical techniques. The two monometallic and two heterobimetallic complexes were evaluated as pre-catalysts for the aqueous biphasic hydro formylation of 1-octene.The mononuclear ferrocenyl complexes were inactive in the aqueous biphasic hydroformylation experiments. Hydroformylation using the heterobimetallic complexes showed that the pre-catalysts are active in 1-octene conversion, yielding aldehydes (linear and branched) as well as isomerisation products (cis and trans 2- and 3-octene). Linear aldehydes were more favoured with the tertiary-butyl analogue of the heterobimetallic complex. Although loss of metal from the aqueous layer was detected using ICP-OES, the catalysts exhibited good recyclability and could be reused up to 4 times.en_ZA
dc.identifier.apacitationSiangwata, S. (2015). <i>Design, synthesis and characterization of water soluble heterobimetallic complexes and their evaluation as aqueous biphasic hydroformylation catalysts</i>. (Thesis). University of Cape Town ,Faculty of Science ,Department of Chemistry. Retrieved from http://hdl.handle.net/11427/16791en_ZA
dc.identifier.chicagocitationSiangwata, Shepherd. <i>"Design, synthesis and characterization of water soluble heterobimetallic complexes and their evaluation as aqueous biphasic hydroformylation catalysts."</i> Thesis., University of Cape Town ,Faculty of Science ,Department of Chemistry, 2015. http://hdl.handle.net/11427/16791en_ZA
dc.identifier.citationSiangwata, S. 2015. Design, synthesis and characterization of water soluble heterobimetallic complexes and their evaluation as aqueous biphasic hydroformylation catalysts. University of Cape Town.en_ZA
dc.identifier.ris TY - Thesis / Dissertation AU - Siangwata, Shepherd AB - A series of new water-soluble N,O-chelating Schiff base ligands were synthesised. These ligands were reacted with ferrocenecarboxaldehyde through Schiff base condensation reactions, leading to new water-soluble ferrocenylimine mononuclear complexes. The mononuclear complexes were reacted with a dimeric rhodium precursor [RhCl(COD)]2 to produce a series of novel ferrocenylimine-Rh(I) heterobimetallic complexes. Both themononuclear and heterobimetallic complexes were found to have good solubility in water of up to 11 mg/mL. The complexes were characterised fully using various spectroscopic and analytical techniques including 1H NMR, 13C NMR spectroscopy, FT-IR spectroscopy, mass spectrometry and elemental analysis. In addition, mononuclear and heterobimetallic complexes were also synthesised as precursors to dendritic DAB-G1 structures. These were found to be water-soluble and they were also characterised using spectroscopic and analytical techniques. The two monometallic and two heterobimetallic complexes were evaluated as pre-catalysts for the aqueous biphasic hydro formylation of 1-octene.The mononuclear ferrocenyl complexes were inactive in the aqueous biphasic hydroformylation experiments. Hydroformylation using the heterobimetallic complexes showed that the pre-catalysts are active in 1-octene conversion, yielding aldehydes (linear and branched) as well as isomerisation products (cis and trans 2- and 3-octene). Linear aldehydes were more favoured with the tertiary-butyl analogue of the heterobimetallic complex. Although loss of metal from the aqueous layer was detected using ICP-OES, the catalysts exhibited good recyclability and could be reused up to 4 times. DA - 2015 DB - OpenUCT DP - University of Cape Town LK - https://open.uct.ac.za PB - University of Cape Town PY - 2015 T1 - Design, synthesis and characterization of water soluble heterobimetallic complexes and their evaluation as aqueous biphasic hydroformylation catalysts TI - Design, synthesis and characterization of water soluble heterobimetallic complexes and their evaluation as aqueous biphasic hydroformylation catalysts UR - http://hdl.handle.net/11427/16791 ER - en_ZA
dc.identifier.urihttp://hdl.handle.net/11427/16791
dc.identifier.vancouvercitationSiangwata S. Design, synthesis and characterization of water soluble heterobimetallic complexes and their evaluation as aqueous biphasic hydroformylation catalysts. [Thesis]. University of Cape Town ,Faculty of Science ,Department of Chemistry, 2015 [cited yyyy month dd]. Available from: http://hdl.handle.net/11427/16791en_ZA
dc.language.isoengen_ZA
dc.publisher.departmentDepartment of Chemistryen_ZA
dc.publisher.facultyFaculty of Scienceen_ZA
dc.publisher.institutionUniversity of Cape Town
dc.subject.otherChemistryen_ZA
dc.titleDesign, synthesis and characterization of water soluble heterobimetallic complexes and their evaluation as aqueous biphasic hydroformylation catalystsen_ZA
dc.typeMaster Thesis
dc.type.qualificationlevelMasters
dc.type.qualificationnameMScen_ZA
uct.type.filetypeText
uct.type.filetypeImage
uct.type.publicationResearchen_ZA
uct.type.resourceThesisen_ZA
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