Structural and reactivity relationships in aryland alkylamine bisphosphine complexes of Tc(I) and Re(I)
| dc.contributor.advisor | Roodt, Andreas | |
| dc.contributor.advisor | Brink, Alice | |
| dc.contributor.author | Kama, Dumisani Vincent | |
| dc.date.accessioned | 2018-09-05T12:19:54Z | |
| dc.date.available | 2018-09-05T12:19:54Z | |
| dc.date.issued | 2018-02 | |
| dc.description.abstract | English: The research project presents the synthesis and evaluation of the radiopharmaceutical model type of fac-[MI(CO)3]+ (M = Re or 99Tc] cores bearing neutral bidentate diphosphinoamine (PNP) ligands. A range of PNP ligands and fac-[M(CO)3(PNP)]+ (M = Re or 99Tc) complexes were prepared using methods described in literature and characterized by means of NMR, IR and Xray crystallography. These ligands were systematically altered in terms of electronic and steric properties. A total of sixteen ligands were evaluated during this study, namely N,N-Bis-(diphenylphosphino)- p-toluidine (1), N,N-Bis(diphenylphosphino)-4-chloroaniline (2), N,NBis( diphenyl-phosphino)-4-fluoroaniline (3), N,N-Bis(diphenylphosphino)-N-Bocethylenediamine (4), N,N-Bis(di-p-tolylphosphino)-p-toluidine (5), N,N-Bis(di-ptolylphosphino)- o-toluidine (6), N,N-Bis(di-p-tolyl-phosphino)cyclobutylamine (7), N,N-Bis(dip- tolylphosphino)cyclohexylamine (8), N,N-Bis(diphenyl-phosphineoxide)-p-toluidine (1a), N,N-Bis(diphenylphosphineoxide)-4-chloroaniline (2a), N,N-Bis(di-phenylphosphineoxide)-4- fluoroaniline (3a), N,N-Bis(diphenylphosphineoxide)-N-Boc-ethylene-diamine (4a), N,N-Bis(dip- tolylphosphineoxide)-p-toluidine (5a), N,N-Bis(di-p-tolylphosphineoxide)-o-toluidine (6a), N,N-Bis(di-p-tolylphosphineoxide)cyclobutylamine (7a) and N,N-Bis(di-p-tolylphosphineoxide) cyclohexylamine (8a). The solid state crystal structures of the ligands pFPh-PhPNP (3), Cbutyl-4-p-tolyl (7), Chzyl-4-ptolyl (8), pFPh-PhPNPO (3a), 5-p-tolyl-PNPO (5a) and Chzyl-4-p-tolyl-PNPO (8a) were reported and described, and revealed various interesting structural conformations. The reported X-ray crystallographic structure determinations further included six rhenium(I) and one technetium-99(I) tricarbonyl complexes namely: fac-[Re(pTol-PhPNP)(CO)3(OiPr)] (1c), fac- [Re(pClPh-PhPNP)(CO)3Br] (2c), fac-[Re(pFPh-PhPNP)(CO)3Br] (3c), fac-[Re(NBoc- PhPNP)(CO)3Br] (4c), fac-[Re(Cbutyl-4-p-tolyl)(CO)3Br] (7c), fac-[Re(Chzyl-4-ptolyl)( CO)3Br] (8c) and fac-[99Tc(Chzyl-4-p-tolyl)(CO)3Cl] (8d) respectively. Four of the reported solid-state rhenium complex structures showed a statistical disorder of the bromido ligand on the apical Br-Re-CO axes. A kinetic study of the formation of fac-[Re(NBoc-PhPNP)(CO)3Br] was conducted utilizing 31P time-resolved NMR. Experimental evidence indicated that the reaction proceeded towards product formation without any significant side reactions. Although limited data was available for this section, acceptable rate laws were identified and proposed, the most feasible consisting of a rapid pre-equilibrium followed by a rate-determining ring-closure by the PNP ligand (K1 = 58(16) M-1, k2 = 0.0013(1) s-1). Preliminary substitution reactions of the bromido ligand in fac- [Re(CO)3(PNP)Br] complexes with entering ligands such as PTA, pyridine and SCN- ions were conducted and the results illustrated that none of the entering ligands could displace the bromine ligand. Preliminary anti-mitochondrial activity of selected non-coordinated PNP ligand namely pTol- PhPNP (1), pClPh-PhPNP (2), pFPh-PhPNP (3) Chzyl-4-p-tolyl (8) and their respective fac- [Re(CO)3(PNP)Br] complexes were tested on Eremothecium ashbyii and Nadsonia fulvescens yeast cells. With the exception of pTol-PhPNP (1), none of the compounds evaluated displayed any cytotoxicity towards the Eremothecium ashbyii and Nadsonia fulvescens yeast cells. | en_ZA |
| dc.description.abstract | Afrikaans: Die navorsingsprojek bied die sintese en evaluasie van die radiofaramaseutiese model tipes met fas-[MI(CO)3]+ (M = Re of 99Tc] kerne draende neutrale difosfinoamien (PNP) ligande aan. ʼn Reeks PNP ligande en fas-[M(CO)3(PNP)]+ (M = Re of 99Tc) komplekse is voorberei volgens metodes soos in die literatuur beskryf, en is gekarakteriseer deur middel van KMR, IR, en Xstraal kristallografie. Hierdie ligande is sistematies verander ten opsigte van elektroniese en steriese eienskappe. ʼn Totaal van sestien ligande naamlik N,N-bis-(di-fenielfosfino)-p-toluïdien (1), N,N-bis(difenielfosfino)-4-chloroanilien (2), N,N-bis(difeniel-fosfino)-4-fluoroanilien (3), N,N-bis(difenielfosfino)-N-boc-etileendiamien (4), N,N-bis(di-p-tolielfosfino)-p-toluïdien (5), N,N-bis(di-p-tolielfosfino)-o-toluïdien (6), N,N-bis(di-p-toliel-fosfino)siklobutielamien (7), N,Nbis( di-p-tolielfosfino)sikloheksielamien (8), N,N-bis(difeniel-fosfienoksied)-p-toluïdien (1a), N,N-bis(difenielfosfienoksied)-4-chloroaniline (2a), N,N-bis(di-fenielfosfienoksied)-4-fluoroaniline (3a), N,N-bis(difenielfosfienoksied)-N-boc-etileendiamien (4a), N,N-bis(di-ptolielfosfienoksied)- p-toluïdien (5a), N,N-bis(di-p-tolielfosfienoksied)-o-toluïdien (6a), N,Nbis( di-p-tolielfosfienoksied)siklobutielamien (7a), en N,N-bis(di-p-tolielfosfienoksied)sikloheksielamien (8a) is gedurende hierdie studie geëvalueer. Die vaste toestand kristalstrukture van die ligande pFPh-PhPNP (3), Cbutiel-4-p-toliel (7), Chzyl-4-p-toliel (8), pFPh-PhPNPO (3a), 5-p-toliel-PNPO (5a) en Chzyl-4-p-toliel-PNPO (8a) is gerapporteer en beskryf, en verskeie interessante strukturele konformasies is onthul. Die gerapporteerde X-straal kristallografiese struktuurbepalings het verder ses renium(I) en een tegnesium-99(I) trikarboniel komplekse ingesluit naamlik: fas-[Re(pTol-PhPNP)(CO)3(OiPr)] (1c), fas-[Re(pClPh-PhPNP)(CO)3Br] (2c), fas-[Re(pFPh-PhPNP)(CO)3Br] (3c), fas-[Re(NBoc- PhPNP)(CO)3Br] (4c), fas-[Re(Cbutiel-4-p-toliel)(CO)3Br] (7c), fas-[Re(Chziel-4-ptoliel)( CO)3Br] (8c), en fas-[99Tc(Chziel-4-p-toliel)(CO)3Cl] (8d). Vier van die gerapporteerde vaste toestand renium kompleks strukture het ʼn statistiese wanorde van die bromido ligand op die apikale Br-Re-CO as vertoon. ʼn Kinetiese studie van die vorming van fas-[Re(NBoc-PhPNP)(CO)3Br] is uitgevoer deur 31P tydgeskeide KMR te benut. Eksperimentele bewyse dui daarop dat die reaksie voortgaan na produkvorming sonder enige beduidende newereaksies. Ten spyte daarvan dat beperkte data vir hierdie afdeling beskikbaar was is aanvaarbare tempowette geïdentifiseer en voorgestel waarvan die mees waarskynlike bestaan uit ʼn vinnige pre-ekwilibrium gevolg deur ʼn tempobepalende ringsluitings deur die PNP ligand (K1 = 58(16) M-1, k2 = 0.0013(1) s-1). Voorlopige substitusiereaksies van die bromido ligand in fas-[Re(CO)3(PNP)Br] komplekse met inkomende ligande soos PTA, piridien en SCN- ione is uitgevoer en die resultate illustreer dat geen van die inkomende ligande die broom ligand kon verplaas nie. Voorlopige antimitokondriale aktiwiteit van uitgesoekte ongekoördineerde PNP ligande naamlik pTol-PhPNP (1), pClPh-PhPNP (2), pFPh-PhPNP (3), en chziel-4-p-toliel (8), asook hulle onderskeie fas-[Re(CO)3(PNP)Br] komplekse is op Eremothecium ashbyii en Nadsonia fulvescens gisselle getoets. Met die uitsondering van pTol-PhPNP (1) toon geen van die geëvalueerde stowwe enige sitotoksisiteit teenoor die Eremothecium ashbyii en Nadsonia fulvescens gisselle nie. | en_ZA |
| dc.description.sponsorship | Swiss National Science Foundation (SNF) | en_ZA |
| dc.description.sponsorship | National Research Foundation (NRF) | en_ZA |
| dc.identifier.uri | http://hdl.handle.net/11660/9242 | |
| 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 | Radiopharmaceutical models | en_ZA |
| dc.subject | Rhenium | en_ZA |
| dc.subject | Technetium | en_ZA |
| dc.subject | Diphosphinoamine | en_ZA |
| dc.subject | Tricarbonyl complexes | en_ZA |
| dc.subject | Formation | en_ZA |
| dc.subject | Substitution | en_ZA |
| dc.subject | Phosphine oxide | en_ZA |
| dc.subject | X-ray crystallography | en_ZA |
| dc.subject | Anti-mitochondrial | en_ZA |
| dc.subject | Thesis (Ph.D. (Chemistry))--University of the Free State, 2018 | en_ZA |
| dc.title | Structural and reactivity relationships in aryland alkylamine bisphosphine complexes of Tc(I) and Re(I) | en_ZA |
| dc.type | Thesis | en_ZA |