{"id":{"repo_id":"cape-town","oai_identifier":"oai:open.uct.ac.za:11427/16791"},"canonical_url":"https://search.dev.ndltd.org/etd/cape-town/oai:open.uct.ac.za:11427/16791","repository":{"repo_id":"cape-town","name":"University of Cape Town","base_url":"https://open.uct.ac.za/oai/request"},"display":{"title":"Design, synthesis and characterization of water soluble heterobimetallic complexes and their evaluation as aqueous biphasic hydroformylation catalysts","abstract":"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.","abstract_html":"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.","abstract_has_math":false,"creators":["Siangwata, Shepherd"],"institution":"Department of Chemistry","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":["Smith, Gregory S","Makhubela, Banothile C E"],"committee_chairs":[],"committee_members":[],"year":2015,"date_issued":"2015","date_published":"2015","updated_at":"2026-07-22T22:22:43Z","subjects":[],"languages":["eng"],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/11427/16791","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Smith, Gregory S","Makhubela, Banothile C E"]},{"key":"dc:creator","label":"Author","values":["Siangwata, Shepherd"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2016-02-05T07:26:15Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2016-02-05T07:26:15Z"]},{"key":"dc:date.issued","label":"Date","values":["2015"]},{"key":"dc:publisher.department","label":"Dc Publisher Department","values":["Department of Chemistry"]},{"key":"dc:publisher.institution","label":"Dc Publisher Institution","values":["University of Cape Town"]},{"key":"dc:type","label":"Dc Type","values":["Master Thesis"]},{"key":"dc:type.qualificationlevel","label":"Dc Type Qualificationlevel","values":["Masters"]},{"key":"dc:type.qualificationname","label":"Dc Type Qualificationname","values":["MSc"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language.iso","label":"Language (ISO)","values":["eng"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["http://hdl.handle.net/11427/16791"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Includes bibliographical references"]},{"key":"dc:description.abstract","label":"Abstract","values":["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."]},{"key":"dc:title","label":"Title","values":["Design, synthesis and characterization of water soluble heterobimetallic complexes and their evaluation as aqueous biphasic hydroformylation catalysts"]}]}],"canonical_facts":{"dc:contributor.advisor":["Smith, Gregory S","Makhubela, Banothile C E"],"dc:creator":["Siangwata, Shepherd"],"dc:date.accessioned":["2016-02-05T07:26:15Z"],"dc:date.available":["2016-02-05T07:26:15Z"],"dc:date.issued":["2015"],"dc:description":["Includes bibliographical references"],"dc:description.abstract":["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."],"dc:identifier.uri":["http://hdl.handle.net/11427/16791"],"dc:language.iso":["eng"],"dc:publisher.department":["Department of Chemistry"],"dc:publisher.institution":["University of Cape Town"],"dc:title":["Design, synthesis and characterization of water soluble heterobimetallic complexes and their evaluation as aqueous biphasic hydroformylation catalysts"],"dc:type":["Master Thesis"],"dc:type.qualificationlevel":["Masters"],"dc:type.qualificationname":["MSc"]},"updated_at":"2026-07-22T22:22:43Z"}