{"id":{"repo_id":"cape-town","oai_identifier":"oai:open.uct.ac.za:11427/22055"},"canonical_url":"https://search.dev.ndltd.org/etd/cape-town/oai:open.uct.ac.za:11427/22055","repository":{"repo_id":"cape-town","name":"University of Cape Town","base_url":"https://open.uct.ac.za/oai/request"},"display":{"title":"Use of water-soluble phosphine ligands in heterogeneous hydroformylation catalysis : application to long-chain 1-alkenes","abstract":"The two-phase rhodium-tri(m-sulfonatophenyl)phosphine (Rh-TPPTS) system for the hydroformylation of 1-octene, 1-decene, and 1-dodecene to the corresponding aldehydes, has been investigated. Due to the two distinct phases - the catalytic species in the aqueous phase and the products and reactants in the organic phase - the separation of the catalyst was easily facilitated. A comparison was made of the activity, selectivity towards linear aldehydes, and catalyst lifetime of two systems where i) the active catalytic species were generated in situ from rhodium trichloride (RhCl₃.3H₂O) and excess phosphine ligand (TPPTS) under mild hydroformylation conditions (5 MPa H₂/CO (1:1); 100 °C); and ii) where the rhodium(I) complex, RhH(CO)(TPPTS)₃ is used as the catalyst precursor. The former system was found to be superior in activity and selectivity to that of the latter, achieving fairly high conversions of ca. 60% for the hydroformylation of 1-octene, with n:iso ratios of up to 16:1 for a catalyst composition a Rh:P ratio of 1:30. Unfortunately low conversions of ca. 10% for the hydroformylation of 1-decene and ca. 4% for that of 1-dodecene resulted under the same conditions. While the reasons for the drastic decrease in conversion for C₁₀ and C₁₂ alkenes is not completely clear, this poor conversion is attributed to the extremely low solubility of the long-chain 1-alkenes in the aqueous phase. Under certain optimum conditions (Rh:P ≥ l :20), virtually no leeching of rhodium into the organic phase was detected. A ³¹P NMR spectroscopic study was undertaken in an attempt to ascertain the nature and distribution of rhodium tertiary-phosphine complexes in the aqueous phase before and after the mixture was subjected to standard hydroformylation conditions.","abstract_html":"The two-phase rhodium-tri(m-sulfonatophenyl)phosphine (Rh-TPPTS) system for the hydroformylation of 1-octene, 1-decene, and 1-dodecene to the corresponding aldehydes, has been investigated. Due to the two distinct phases - the catalytic species in the aqueous phase and the products and reactants in the organic phase - the separation of the catalyst was easily facilitated. A comparison was made of the activity, selectivity towards linear aldehydes, and catalyst lifetime of two systems where i) the active catalytic species were generated in situ from rhodium trichloride (RhCl₃.3H₂O) and excess phosphine ligand (TPPTS) under mild hydroformylation conditions (5 MPa H₂/CO (1:1); 100 °C); and ii) where the rhodium(I) complex, RhH(CO)(TPPTS)₃ is used as the catalyst precursor. The former system was found to be superior in activity and selectivity to that of the latter, achieving fairly high conversions of ca. 60% for the hydroformylation of 1-octene, with n:iso ratios of up to 16:1 for a catalyst composition a Rh:P ratio of 1:30. Unfortunately low conversions of ca. 10% for the hydroformylation of 1-decene and ca. 4% for that of 1-dodecene resulted under the same conditions. While the reasons for the drastic decrease in conversion for C₁₀ and C₁₂ alkenes is not completely clear, this poor conversion is attributed to the extremely low solubility of the long-chain 1-alkenes in the aqueous phase. Under certain optimum conditions (Rh:P ≥ l :20), virtually no leeching of rhodium into the organic phase was detected. A ³¹P NMR spectroscopic study was undertaken in an attempt to ascertain the nature and distribution of rhodium tertiary-phosphine complexes in the aqueous phase before and after the mixture was subjected to standard hydroformylation conditions.","abstract_has_math":false,"creators":["Du Toit, Judith G O"],"institution":"Department of Chemistry","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":["Koch, Klaus R"],"committee_chairs":[],"committee_members":[],"year":1994,"date_issued":"1994","date_published":"1994","updated_at":"2026-07-22T22:22:47Z","subjects":[],"languages":["eng"],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/11427/22055","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Koch, Klaus R"]},{"key":"dc:creator","label":"Author","values":["Du Toit, Judith G O"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2016-10-03T04:10:05Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2016-10-03T04:10:05Z"]},{"key":"dc:date.issued","label":"Date","values":["1994"]},{"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/11427/22055"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["The two-phase rhodium-tri(m-sulfonatophenyl)phosphine (Rh-TPPTS) system for the hydroformylation of 1-octene, 1-decene, and 1-dodecene to the corresponding aldehydes, has been investigated. Due to the two distinct phases - the catalytic species in the aqueous phase and the products and reactants in the organic phase - the separation of the catalyst was easily facilitated. A comparison was made of the activity, selectivity towards linear aldehydes, and catalyst lifetime of two systems where i) the active catalytic species were generated in situ from rhodium trichloride (RhCl₃.3H₂O) and excess phosphine ligand (TPPTS) under mild hydroformylation conditions (5 MPa H₂/CO (1:1); 100 °C); and ii) where the rhodium(I) complex, RhH(CO)(TPPTS)₃ is used as the catalyst precursor. The former system was found to be superior in activity and selectivity to that of the latter, achieving fairly high conversions of ca. 60% for the hydroformylation of 1-octene, with n:iso ratios of up to 16:1 for a catalyst composition a Rh:P ratio of 1:30. Unfortunately low conversions of ca. 10% for the hydroformylation of 1-decene and ca. 4% for that of 1-dodecene resulted under the same conditions. While the reasons for the drastic decrease in conversion for C₁₀ and C₁₂ alkenes is not completely clear, this poor conversion is attributed to the extremely low solubility of the long-chain 1-alkenes in the aqueous phase. Under certain optimum conditions (Rh:P ≥ l :20), virtually no leeching of rhodium into the organic phase was detected. A ³¹P NMR spectroscopic study was undertaken in an attempt to ascertain the nature and distribution of rhodium tertiary-phosphine complexes in the aqueous phase before and after the mixture was subjected to standard hydroformylation conditions."]},{"key":"dc:title","label":"Title","values":["Use of water-soluble phosphine ligands in heterogeneous hydroformylation catalysis : application to long-chain 1-alkenes"]}]}],"canonical_facts":{"dc:contributor.advisor":["Koch, Klaus R"],"dc:creator":["Du Toit, Judith G O"],"dc:date.accessioned":["2016-10-03T04:10:05Z"],"dc:date.available":["2016-10-03T04:10:05Z"],"dc:date.issued":["1994"],"dc:description.abstract":["The two-phase rhodium-tri(m-sulfonatophenyl)phosphine (Rh-TPPTS) system for the hydroformylation of 1-octene, 1-decene, and 1-dodecene to the corresponding aldehydes, has been investigated. Due to the two distinct phases - the catalytic species in the aqueous phase and the products and reactants in the organic phase - the separation of the catalyst was easily facilitated. A comparison was made of the activity, selectivity towards linear aldehydes, and catalyst lifetime of two systems where i) the active catalytic species were generated in situ from rhodium trichloride (RhCl₃.3H₂O) and excess phosphine ligand (TPPTS) under mild hydroformylation conditions (5 MPa H₂/CO (1:1); 100 °C); and ii) where the rhodium(I) complex, RhH(CO)(TPPTS)₃ is used as the catalyst precursor. The former system was found to be superior in activity and selectivity to that of the latter, achieving fairly high conversions of ca. 60% for the hydroformylation of 1-octene, with n:iso ratios of up to 16:1 for a catalyst composition a Rh:P ratio of 1:30. Unfortunately low conversions of ca. 10% for the hydroformylation of 1-decene and ca. 4% for that of 1-dodecene resulted under the same conditions. While the reasons for the drastic decrease in conversion for C₁₀ and C₁₂ alkenes is not completely clear, this poor conversion is attributed to the extremely low solubility of the long-chain 1-alkenes in the aqueous phase. Under certain optimum conditions (Rh:P ≥ l :20), virtually no leeching of rhodium into the organic phase was detected. A ³¹P NMR spectroscopic study was undertaken in an attempt to ascertain the nature and distribution of rhodium tertiary-phosphine complexes in the aqueous phase before and after the mixture was subjected to standard hydroformylation conditions."],"dc:identifier.uri":["http://hdl.handle.net/11427/22055"],"dc:language.iso":["eng"],"dc:publisher.department":["Department of Chemistry"],"dc:publisher.institution":["University of Cape Town"],"dc:title":["Use of water-soluble phosphine ligands in heterogeneous hydroformylation catalysis : application to long-chain 1-alkenes"],"dc:type":["Master Thesis"],"dc:type.qualificationlevel":["Masters"],"dc:type.qualificationname":["MSc"]},"updated_at":"2026-07-22T22:22:47Z"}