Synthetic, kinetic and electrochemical studies on new osmocene-containing betadiketonato rhodium(I) complexes with biomedical applications
| dc.contributor.advisor | Swarts, J. C. | |
| dc.contributor.author | Ambrose, Zeldene Salomy | |
| dc.date.accessioned | 2018-07-17T08:49:14Z | |
| dc.date.available | 2018-07-17T08:49:14Z | |
| dc.date.issued | 2006-06 | |
| dc.description.abstract | Afrikaans: Nuwe osmoseen-bevattende β-diketone, 1-osmocenyl-4,4,4-trifluorobutan-1,3-dione [Hoctfa, pKa/= 7.90(2)], 3, 1-osmocenylbutane-1,3-dione [Hoca, pKa/= 10.39(3)], 4,1-osmocenyl-3-phenylpropane-1,3-dione [Hbocm, pKa/= 10.59(2)],), 5, 3-ferrocenyl-1- osmocenylpropane-1,3-dione [Hocfcm, pKa/=13.04(1)], 6, 1-osmocenyl-3-ruthenocenylpropane-1,3-dione [Hocrcm, pKa/=11.42(1)], 7 en 1-osmocenyl-1,3- propanedione [Hoch, pKa/=7.54(3)], 8, is berei deur die Claisen kondensasie van asetielosmoseen en die toepaslike ester onder die invloed van litiumdiisopropielamied. Waar moontlik is resultate vergelyk met die toepaslike R-groep elektronegatiwitiet van die onderskeie komplekse bestudeer in die studie. Die [Rh(β-diketonato)(cod)]-komplekse, [Rh(octfa)(cod)], 12, [Rh(oca)(cod)], 13, [Rh(bocm)(cod)], 14, [Rh(ocfcm)(cod)], 15, en [Rh(och)(cod)],16, is berei vanaf die reaksie tussen die toepaslike osmocene β-diketone en [Rh2(cod)2Cl2]. ‘n Kinetiese studie van enol-keto isomerisasie vir die β-diketone Hoctfa, 3, Hoca, 4, Hbocm, 5, Hocfcm, 6, en Hocrcm, 7 , is met behulp van 1H KMR spektroskopie bestudeer. Dit was gevind dat die snelheid van enol-keto isomerisasie elektronies deur die β-diketoon sy-groepe beinvloed word. Dit word aangetoon dat die isomerisasie kinetika versnel volgens die reeks CF3 > C6H5 > CH3 > Fc > Rc. Die isomerisasie kinetika vir keto-enol omskakeling vir die β-diketoon Hoca, 4, is ook met behulp van 1H KMR spektroskopies bestudeer. Kinetiese resultate vir die substitusie van die β-diketonato ligand van die Rh(β- diketonato)(cod)] komplekse [Rh(octfa)(cod)], [Rh(oca)(cod)], [Rh(bocm)(cod)], [Rh(ocfcm)(cod)] en [Rh(och)(cod)]) met 1,10-fenantrolien in metanol word ook aangebied. Die groot negatiewe entropie waardes wat verkry is, dui op ‘n assosiatiewe substitusie meganisme. Oksidasiepotensiale (Epa waardes vs. Ag/Ag+) van die osmium kern in die vry β-diketone (Hoctfa, Hoca, Hbocm, Hocfcm, Hocrcm en Hoch), en in die [Rh(β-diketonato)(cod)] komplekse, ([Rh(octfa)(cod)], [Rh(oca)(cod)], [Rh(bocm)(cod)], [Rh(ocfcm)(cod)] en [Rh(och)(cod)]) is bepaal. Die piek oksidasiepotensiale (Epa waardes vs. Ag/Ag+) vir die oksidasie van die rhodium(I) kern is ook bepaal. | en_ZA |
| dc.identifier.uri | http://hdl.handle.net/11660/8743 | |
| dc.language.iso | en | en_ZA |
| dc.publisher | University of the Free State | en_ZA |
| dc.rights.holder | University of the Free State | en_ZA |
| dc.subject | Rhodium | en_ZA |
| dc.subject | Group electrons | en_ZA |
| dc.subject | Osmocene | en_ZA |
| dc.subject | Electrochemical | en_ZA |
| dc.subject | β-diketonato | en_ZA |
| dc.subject | Chemical kinetics | en_ZA |
| dc.subject | Dissertation (M.Sc. (Chemistry))--University of the Free State, 2006 | en_ZA |
| dc.title | Synthetic, kinetic and electrochemical studies on new osmocene-containing betadiketonato rhodium(I) complexes with biomedical applications | en_ZA |
| dc.type | Dissertation | en_ZA |