Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2005. / This study comprises the preparation and characterisation of completely new Fischer-type carbene complexes of chromium and tungsten by deprotonation of (CO)5M=C(NMe2)(Me), (CO)5M=C(OMe)(Me) or (CO)5M=C(NMe2)C≡CH, and subsequent treatment of the formed anion with a variety of reagents, including reactive metal complexes. The deprotonation of the termodynamically stable complexes, (CO)5M=C(NMe2)(Me) (M = Cr or W) followed by reaction with the sulfonium salt, [Me2(MeS)S][BF4], yielded not only the expected products (CO)5M=C(NMe2)CH2SCH3, but also thioether complexes, (CO)5MS(CH3)2, disulfinated complexes (CO)5M=C(NMe2)CH(SCH3)2, S-bridged dinuclear compounds (CO)5M=C(NMe2)CH2S(CH3)M(CO)5, as well as the unique fourmembered- C,S-chelate carbene complexes (CO)4Cr=C(NMe2)CH(SCH3)SCH3 and (CO)4M=C(NMe2)CH2SCH3. Crystal structure determinations of (CO)5W=C(NMe2)CH(SCH3)2, (CO)5Cr=C(NMe2)CH2S(CH3)Cr(CO)5, (CO)4M=C(NMe2)CH2SCH3 (M = Cr, W) and (CO)4Cr=C(NMe2)CH(SCH3)SCH3 were successfully performed. The latter tetracarbonyl complexes have Cr-S bonding distances of 2.4531(9) and 2.4517(5) Å and a W-S distance of 2.577(1) Å. These relatively weak bonds contribute to the short M-C(O)-distances trans to it. The formed four membered chelate rings are essentially planar. The deprotonation of (CO)5Cr=C(NMe2)(Me) and sequential reaction with sulphur and CF3SO3Me does not yield the expected product, (CO)5Cr=C(NMe2)CH2SCH3, but (CO)5CrS=C(NMe2)CH3 resulting from a sulphur insertion was isolated. A single crystal structure determination of the latter complex shows a normal thione carbene complex. The reaction of methyl(methoxy)carbenepentacarbonylchromium(0) and the tungsten analogue with n-BuLi, followed by reaction with [Me2(MeS)S][BF4], afforded unexpected complexes via an unusual addition dissimilar to the above mentioned reactions of dimethylaminocarbene complexes. The formation of the products, (CO)5M=C(OMe)[CH=C(Me)NH(Me)] and (CO)4M=C(OMe)[C(SMe)=C(Me)NH(Me)] (M = Cr, W) can be ascribed to the influence of the heteroatom, oxygen, as well as the presence of acetonitrile in the sulfonium salt reagent [Me2(MeS)S][BF4]. An unusual alkylation by Me+ is also affected. The X-ray crystallographic structure determination of the complexes show hydrogen bonding between the alkoxy oxygen atoms and the protons on the nitrogen atoms. The latter four membered C,S-chelates show bonding distances and angles similar to these of the previously mentioned four membered chelates. Deprotonation of the alkynyl carbene complexes, (CO)5M=C(NMe2)C≡CH (M = Cr, W), with n-BuLi and subsequent reaction with PPh3AuX (X = Cl, NO3), initially afford the β-transmetalated products (CO)5M=C(NMe2)C≡CAuPPh3. In solution (CH2Cl2) the product isomerises through metal migration to Ph3PAuC(NMe2)=C=C=W(CO)5. The conversion was followed by means of 1H-NMR-spectroscopy and it appears that two first order reactions take place consecutively.

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2008. / In this study, the coordination of certain Group 6 and Group 10 & 11 metals to Odonor and S-donor ligands were investigated. For the most part, this involved the isolation of new Mo(VI) and W(VI) complexes. By using a distribution diagram that shows the dependence of the type of species in solution with pH, we attempted to crystallize new polyoxoanion species of the two metals. It was found that the products that crystallize are not necessarily dependant upon the relative concentrations of the species in solution, but rather on the effective packing of the crystal types that are prepared. During this study a unique W(VI) polyanion, [(CH3CH2)4N]2[W6O19] (4), was isolated. The Mo(VI) analogue of this compound as well as the dinuclear Mo(VI)-W(VI) complex have been reported previously, but a pure W(VI) compound of this type has not been successfully isolated yet. A new polymorph of a known dimolybdate, K2Mo2O7·H2O (1), was also crystallized, even though dimolybdate species do not generally occur in solution. This structure, although previously reported, shows some differences with the one in the literature, in particular large deviations in unit cell dimensions. Subsequently, as a second component of this study, a variety of carboxylates were coordinated to Mo(VI) and W(VI) species in an acidic medium. Two new complexes of Mo(VI) with these carboxylate ligands were isolated: [(CH3CH2)4N][MoO3(mal)]·H2O (5) (mal = malate) and Na6[Mo2O5(cit)2] (6) (cit = citrate). The ligands are two- and threefold deprotonated respectively and coordinate in a polydentate manner to the metal centra. The formation of compound 5 in solution has been known for many years, but the structure of this complex has not been determined in the solid state until now. Also, the tungsten analogue of compound 6 was reported years ago, but the Mo(VI) complex has not been crystallized before. Compounds 5 and 6 exhibit a 1:1 and 2:2 metal to ligand ratio respectively, and these ratios are quite rare in Mo(VI) crystal chemistry. Finally, the dimolybdate complex, [CH3)3N(CH2)6N(CH3)3][Mo2O7(cit)] (7), was isolated, and its structure determined and compared to the one in the literature. In the third part of this study, our attention shifted to the group 10 and 11 metals, platinum and gold. Attempts were made to coordinate unusual ligands with donor atoms P, Se and/or S to these metal centers. During this investigation, we isolated a unique Pt(IV) complex, PtCl2(S3C8H7)2 (9). The structure of this compound that was determined crystallographically involves the coordination of two identical R-SCS2 fragments to the metal ion forming four-membered chelate rings. No compounds of Pt and Au with the P-Se ligand, P3Se3(C(C6H5)3)3, could be isolated. However, a mixed valence compound of Au(I,III), [Au(I)Cl(S(CH2C6H5)2)][Au(III)Cl3(S(CH2C6H5)2] (8), could be isolated and characterized. In this compound Au exhibits two oxidation states, +1 and +3. Although the complex has been reported previously, the structure was not described fully, and we now unequivocally determined its crystal structure. The extended structure shows the formation of chains of alternating Au(I) and Au(III) centers with a separation of 5.610 Å.

Thesis (MSc)--Stellenbosch University, 2004. / ENGLISH ABSTRACT: Two new potentially biodegradable aminopolycarboxylic acid ligands, iminodiglutaric acid tetra sodium salt (IDG-4Na) and iminoglutaricsuccinic acid tetra sodium salt (IGS- 4Na), were synthesized in reasonably good yield and purity. The commercially unavailable precursor for the two ligands, ethyl p-aminoglutarate, was synthesised in high yield and purity, and together with the two ligands were fully characterized by means of melting point measurements and various spectrometric techniques CH-NMR, 13C-NMR, MS and IR). For the first time, an electrochemical study has been conducted on the complexes of these ligands with selected transition metal ions (Zn2+, Cu2+ and Cd2+). An electrochemical technique, cyclic voltammetry (CV), was utilized on the study of the complexing ability of the ligands to the selected metal ions. An electrochemical cell comprising three electrodes was employed: thin film mercury coated carbon microelectrode was used as the working electrode, a Platinum wire as the auxiliary electrode, and a Ag/AgCI as the reference electrode. CV has been used and proven to offer a convenient route towards the determination of metal-ligand complex stability constants in aqueous media". The values of the logarithms of the metal-ligand formation constants obtained by this technique, when compared with other widely used aminopolycarboxylic acids (APCAs), show better complexing ability of the ligands with the transition metal ions. When the two ligands are compared, IGS showed greater affinity towards the selected transition metal ions. This is due to the fact that, in aqueous media, as the side chain ligators decrease, the stabilization energy of the complex increases. The formation stability constants were determined by plotting the change in the reduction potential (ΔE) against solution pH. A process making use of a modification of lingane equation was used. / AFRIKAANSE OPSOMMING: Twee nuwe potensieel bio-afbreekbare amienpolikarboksielsuurligande, iminobiglutaarsuur -tetranatriumsout (IBG-4Na) en iminoglutaarsuksiensuurtetranatriumsout (IGS-4Na), was vervaardig met redelike goeie opbrengs en suiwerheid. Die kommersïeel onverkrygbare voorloper van die twee ligande, etiel-B-aminoglutaraat, was berei met hoë obrengs en suiwerheid, en was saam met die twee ligande ten volle geïdentifiseer deur middel van smeltpunt bepalings en verskeie spektrometriese tegnieke CH-KMR, 13C-KMR, MS en IR.). Vir die eerste keer is 'n elektrochemiese studie uitgevoer op die komplekse van hierdie ligande met selektiewe oorgangsmetaalione (Zn2+, Cu2+, en Cd2+). 'n Elektrochemiese tegniek, sikliese voltametrie (SV), is gebruik om die komplekseringsvermoë van die ligande ten opsigte van die geselekteeerdr metaalione te bestudeer. 'n Elektrochemiese sel wat bestaan uit drie elektrodes is gebruik: 'n Dunlaag kwikelektrode bedek met koolstof is gebruik as die werkselektrode, 'n platinumdraad as die bykomende elektrode en 'n Ag/AgCI elektrode as die verwysingselektrode. SV is voorheen gebruik en bewys as 'n gerieflike metode vir die bepaling van metaalligandkompleksstabiliteitskonstantes in waterige media'. Die waardes van die logaritmes van die metaalligandvormingskonstantes wat verkry word deur hierdie tegniek, soos vergelyk met ander algemeen gebruikte amienpolikarboksielsure (APKSe), vertoon beter komplekseringsvermoë met die ligande deur middel van die oorgangsmetaalione. Wanneer die twee ligande met mekaar vergelyk word, het IGS-4Na groter affiniteit gehad vir die oorgangsmetaalione. Dit is as gevolg van die feit dat die stabiliteitsenergie van die kompleks in waterige media verminder word soos wat die sykettings van die ligande toeneem. Die vormingstabilitietskonstantes was bepaal deur 'n varandering in reduksie potensiaal (ΔE) teenoor die pH van die oplossings te plot. Die grafieke is verkry deur 'n aanpassing van die Lingnane-vergelyking te gebruik.

Dissertation (PhD)--University of Stellenbosch, 2003. / ENGLISH ABSTRACT: This study comprises the preparation and characterisation of various novel organometallic species of gold(I) by employing a range of anionic group 6 metal Fischer-type carbene complexes and group 6 metal-acyl complexes as synthons of the organic moieties introduced to the gold(I) electrophiles. The main objectives of this work are to develop the use of Fischer-type carbene complexes as synthons in the preparation of novel organometallic species along unusual reaction pathways and, in doing so, to expand the organometallic chemistry of gold(I), especially Au-C bond formation reactions. By reacting various β-CH acidic Fischer-type alkoxy/dialkylamino/ alkthio(methyl)carbene complexes, first with a base, and then with a gold(I) electrophile (Ph3PAu+), easy access to vinyl ether/dialkylamine/thioether complexes of gold(I) coordinated to M(CO)5 (M = Cr, Mo, W) fragments, is obtained. When methyl alkoxy- or dialkylaminocarbene complexes are employed, coordination of the novel alkoxyvinyl-gold(I)PPh3 and dialkylaminovinyl-gold(I)PPh3 species to the M(CO)5 fragments occurs in an asymmetrical fashion through the vinyl functionalities of the novel gold(I) species. This usually unstable coordination mode for vinyl ethers is stabilised by delocalisation of partial positive charges from the α-gold vinyl carbon atoms to either the gold(I)PPh3 fragment [for η2-{alkoxyvinyl-gold(I)PPh3}M(CO)5 complexes] or the nitogen atoms of the vinyl amine group [for η2-{dialkylaminovinylgold( I)PPh3}M(CO)5 complexes]. In the latter complexes this delocalisation occurs to such an extent that these complexes are best described as zwitterions. The corresponding negative charges in the bimetallic complexes reside on the M(CO)5 fragments. As a representative example, uncoordinated ethoxyvinyl-gold(I)PPh3 was isolated in high yield via a ligand replacement reaction with PPh3. When Fischer-type alkthio(methyl)carbene complexes are employed in this conversion, novel sulphur coordinated {alkthiovinyl-gold(I)PPh3}Cr(CO)5 complexes are formed.The reaction mechanism involved in these conversions is believed to be the gold(I) analogue of the hydrolysis of Fischer-type carbene complexes. In this mechanism the bimetallic η2-vinyl ether coordinated {alkoxyvinyl-gold(I)PPh3}M(CO)5 complexes represent stabilised gold(I) analogues of postulated transition states in the hydrolytic decomposition of Fischer-type alkoxycarbene complexes. The term aurolysis is conceived to describe the conversion when Ph3PAu+ is employed as electrophile instead of H+. The formation of the bimetallic η2-vinyl ether coordinated complexes in the current conversion, furthermore, strongly supports the existence of similar transition states in the hydrolytic decomposition of Fischer-type alkoxycarbene complexes. This mechanism is also accepted for the formation of analogous η2-{dialkylaminovinyl-gold(I)PPh3}M(CO)5 and {alkthiovinyl-gold(I)PPh3}-S Cr(CO)5 complexes when β-CH deprotonated Fischer-type dialkylamino- and alkthiocarbene complexes are employed in this reaction. The reaction of anionic group 6 metal-acyl complexes and their nitrogen analogues, N-deprotonated Fischer-type aminocarbene complexes, leads to the formation of acylgold(I) and novel imidoylgold(I) complexes coordinated to M(CO)5 (M = Cr, W) fragments. In the previous complexes poor stabilisation of the M(CO)5 fragments allows halide anions to readily form ionic adducts with these groups. This characteristic of these products provides a useful reaction pathway to the first example of a free acylgold(I) complex, benzoyl-AuPPh3. Coordination of the imine nitrogen atom to the M(CO)5 fragments in the analogous bimetallic imidoylgold(I)-M(CO)5 complexes is much stronger. These complexes are remarkably stable and could even be effectively isolated by means of low temperature silica gel chromatography. As a preliminary reaction mechanism for this conversion we propose a mechanism that is closely related to the aurolysis mechanism described above. The only difference is that, instead of formal reductive elimination of vinyl ethers/amine/thioether complexes of gold(I) from the M(CO)5 fragments, acyl and imidoyl complexes of gold(I) are produced in this step. Furthermore, the (Z)- stereoisomers of the bimetallic imidoylgold(I)-M(CO)5 complexes generated in this conversion are exclusively obtained.A second N-deprotonation-auration reaction sequence performed on suitable examples of the bimetallic imidoylgold(I)-M(CO)5 complexes yields, as the only isolable product, a novel triangular Au2Cr cluster complex, cis-{η2-(Ph3PAu)2} PPh3Cr(CO)4. This complex is the isolobal equivalent for the unstable molecular hydrogen complex, (η2-H2)PPh3Cr(CO)4, and exhibits the shortest known Au-Au separation between two gold atoms in cluster complexes of the type Au2M. Finally, two novel and vastly different molecular structures of closely related anionic benzoylpentacarbonyl tungstates, one with Li+ as counterion and another in which exactly half the Li+-cations have been replaced by protons, highlight the importance of hydrogen bonding and ion-dipole interactions in determining the solid state structure of such complexes. / AFRIKAANSE OPSOMMING: Hierdie studie behels die bereiding en karakterisering van verskeie nuwe organometaalkomplekse van goud(I). Hierdie komplekse is berei deur gebruik te maak van n wye reeks anioniese groep 6 metaal Fischer-tipe karbeenkomplekse asook anioniese groep 6 metaal asielkomplekse as sintetiese ekwivalente vir die organiese fragmente wat gedurende die sintese aan die goud atoom gebind word. Die hoofdoel van hierdie studie is om die gebruik van Fischer-tipe karbeenkomplekse as sintetiese voorgangers in die bereiding van nuwe organometaalverbindings te ontwikkel en om sodoende ook die organometaalchemie van goud verder uit te bou. Veral die ontwikkeling van nuwe sintetiese metodologieë vir die bereiding van Au-C bindings is hier van belang. Verskeie Fischer-tipe alkoksie-/dialkielamino-/alktio-(metiel)karbeenkomplekse met suuragtige waterstofatome geleë op die β-metallo-koolstofatoom is eers onomkeerbaar gedeprotoneer. Byvoeging van die goud(I) elektrofiel, Ph3PAu+, lei - volgens n ongewone reaksiemeganisme - tot die vorming van onderskeie vinieleter-, dialkielvinielamien- en vinieltioeterkomplekse van goud(I). Hierdie komplekse is verder ook op verskillende wyses aan M(CO)5 fragmente (M = Cr, Mo, W) gekoördineer. Die vinieleter- en vinielamienkomplekse van goud(I), wat vorm wanneer alkoksie- en dialkielaminokarbeenkomplekse onderskeidelik in hierdie sintese aangewend word, koördineer onsimmetries deur hulle viniel dubbelbindings aan die vrygestelde M(CO)5-groepe. Hierdie normaalweg onstabiele vorm van vinieleterkoördinasie, word gestabiliseer deur delokalisering van positiewe lading vanaf die α-goud viniel koolstofatoom na die AuPPh3-fragment [vir die η2-{alkoksievinielgoud( I)PPh3}M(CO)5 komplekse] óf na die stikstofatoom van die dialkielvinielamien groep [vir die η2-{dialkielaminoviniel-goud(I)PPh3}M(CO)5 komplekse]. Laasgenoemde komplekse kan as zwitterione beskryf word. Die onderskeie negatiewe ladings in hierdie komplekse bevind hulle hoofsaaklik op die M(CO)5 groepe. Sterk koördinerende ligande (bv. PPh3) verplaas die onsimmetriese viniel eter vanaf die M(CO)5-fragment. Só kon, as n voorbeeld, die vrye etoksievinielgoud( I)PPh3-kompleks met n hoë opbrengs berei word. Wanneer β-gedeprotoneerdeFischer-tipe tiokarbeenkomplekse met Ph3PAu+ reageer, vorm swawel gekoördineerde {tioviniel-goud(I)PPh3}Cr(CO)5 bimetalliese komplekse in stede van die π-komplekse. Dit word voorgestel dat in die bogenoemde reaksies die goud(I)elektrofiel dieselfde rol vervul as die proton gedurende die hidrolise van Fischer-tipe alkoksiekarbeenkomplekse. Die bimetalliese, η2-vinieleter-gekoördineerde {alkoksieviniel-goud(I)PPh3}M(CO)5-komplekse hier berei verteenwoordig dus stabiele goud(I) analoë van voorgestelde tusseprodukte in so ’n meganisme. Die term aurolise word voorgestel om die geval waar Ph3PAu+ in stede van H+ as elektrofiel aangewend word te beskryf. Die vorming van bimetalliese, η2-vinieletergeko ördineerde komplekse in die huidige reaksie ondersteun die moontlike vorming van die voorgestelde tussenprodukte tydens die hidrolise van Fischer-tipe alkoksie(metiel)karbeenkomplekse. ’n Soortgelyke meganisme kan ook gebruik word om die vorming van die η2-{dialkiellamienviniel-goud(I)PPh3}M(CO)5- en {alktioviniel-goud(I)PPh3}-S Cr(CO)5-komplekse vanuit β-CH gedeprotoneerde Fischer-tipe dialkielamino- en tiokarbeenkomplekse en Ph3PAuCl te interpreteer. Die reaksie van anioniese groep 6 oorgangsmetaal metaal-asielkomplekse en hulle stikstofanaloë, N-gedeprotoneerde Fischer-tipe aminokarbeenkomplekse, lewer onderskeidelik asiel- en imidoielkomplekse van goud(I) wat aan M(CO)5 fragmente (M = Cr, W) koördineer. Die goud(I)asiel-M(CO)5 koördinasie deur die asielsuurstofatoom is baie swak en die M(CO)5-eenheid in hierdie komplekse word maklik deur haliedanione en sekere oplosmiddel molekules verplaas. Die haliedanione vorm anioniese addukte met the M(CO)5 fragmente. Hierdie eienskap van die bimetalliese komplekse verskaf sodoende n gerieflike sintetiese roete na die eerste voorbeeld van n vrye asielgoud(I)-kompleks, bensoiel-AuPPh3. Koördinasie van die imienstikstofatoom aan M(CO)5-groepe in die bg. imidoielkomplekse is egter veel sterker. Die bimetalliese {imidoielgoud(I)}M(CO)5-komplekse is verbasend stabiel en kan selfs effektief deur middel van lae temperatuur SiO2-kolomkromatografie geïsoleer word. n Soortgelyke reaksie meganisme as wat voorgestel word vir die aurolise van Fischer-tipe karbeenkomplekse word voorgestel vir hierdie reaksie. Die enigste verskil is dat die formele reduktiewe eliminasie van n viniel-eter, -amien of -tioeter vervang word met die vorming van asiel- of imidoielkomplekse van goud(I). Verder word die (Z)-isomere van die bimetalliese {imidoielgoud(I)}M(CO)5-komplekse uitsluitlik in hierdie reaksie verkry. Wanneer geskikte voorbeelde van bimetalliese {imidoielgoud(I)}M(CO)5-komplekse n tweede keer gedeprotoneer word en gereageer word met Ph3PAuCl, is die enigste isoleerbare produk van die reaksie n driehoekige Au2Cr troskompleks, nl. cis-{η2- (Ph3PAu)2}PPh3Cr(CO)4. Hierdie verbinding dien as n isolobale model vir die onstabiele molekulêre waterstof kompleks , (η2-H2)PPh3Cr(CO)4, en besit verder die kortste Au-Au afstand tussen twee goud atome in driehoekige troskomplekse wat nog tot dusvêr gerapporteer is. Laastens is die kristalstrukture van twee nou verwante anioniese {bensoiel}W(CO)5- komplekse bepaal. Die enigste verskil tussen die hierdie twee verbindings is dat die een slegs Li+ as teenioon bevat terwyl presies die helfte van die Li+-teenione in die tweede struktuur deur protone verplaas is. Hierdie klein verskil in samestelling veroorsaak egter drastiese verskille in die kristalstrukture van hierdie verbindings. Die belangrikheid van waterstof bindings en ioon-dipool interaksies in die bepaling van die vastetoestandstrukture van sulke verbindings word hierdeur beklemtoon.

Dissertation (PhD)--University of Stellenbosch, 2005. / ENGLISH ABSTRACT: DFT calculations employing the B3LYP functional were done to investigate the mechanism for the Ni-catalyzed hydrocyanation of ethylene as proposed by Tolman. Although this reaction is an important industrial process, its mechanism has never been studied computationally, apart from calculations pertaining to ligand tailoring. This study comprises a detailed configurational analysis of each step of the reaction cycle, charge decomposition analysis of pertinent species and analysis of the activation barriers involved at each step. A model ligand, PH3, is employed, due to its electronic similarity to the experimental ligand most widely used, P(O-o-tolyl)3, and its small size, which makes it amenable for calculations at this level. It was found that oxidative addition of HCN to the precursor complex (ethylene)NiL2 (L=PH3) can take place in one step and that it is the rate-determining step in the gas phase. The resulting adduct has H+ (which becomes a hydride) and CN- coordinated in the cis configuration. Ligand dissociation yields three configurations of (ethylene)-NiHCNL, of which only two can participate in the catalytic cycle. It is shown that this is because migration-insertion of ethylene into the Ni-H bond takes place before, or concomitant with, association of a second ethylene molecule, contrary to expectation. This path therefore requires that ethylene and hydrogen are coordinated in the cis configuration, something only possible for two of the three isomers of (ethylene)NiHCNL. The calculations support the mechanism of associative reductive elimination and shows that elimination can only take place if the ethyl and cyanide groups are in the cis configuration. Analysis of the energetic profile of the reaction shows that entropy effects play a very important role in the propagation of the cycle, at least in the gas phase. Preliminary work on the effect of Lewis acids the catalytic cycle is presented, with structural and energetic analysis. An important general conclusion is that the standard way of representing the energy profile of reactions where intermolecular transitions (as opposed to intramolecular transitions only) take place can be misleading. It will be argued that the implicit assumption that two species which are minimum energy structures on distinct potential energy surfaces will also be an energy minimum on one potential energy surface skews the energy profile of the reaction. The consequence of this is that care must be taken in representing energy profiles for reactions where more than one distinct species participates. / AFRIKAANSE OPSOMMING: Die meganisme, soos deur Tolman voorgestel, van die Ni-gekataliseerde hidrosianering van etileen word ondersoek met behulp van Kohn-Sham elektrondigtheidsteorie (density finctional theory, DFT) berekeninge waarin die B3LYP-funksionaal gebruik word. Alhoewel die reaksie ‘n belangrike proses is in die industrie, is die volle me-ganisme nog nooit met behulp van berekeninge bestudeer nie. Daar is egter wel al werk gedoen aangaande sekere aspekte van die reaksie, byvoorbeeld ligandontwerp. Hierdie studie behels ‘n noukeurige konfigurasionele analise van elke stap van die reaksie-siklus, ladingsverdelingsanalise (charge decomposition analysis, CDA) van sekere belangrike spesies asook die analise van die energiestappe betrokke by elke stap. Fosfien is gekies as ‘n modelligand, omdat dit elektronies ooreenstem met P(O-o-toliel)3, die ligand wat meestal in eksperimentele werk gebruik is. Die klein grootte van fosfien maak dit ook geskik vir be-rekeninge op hierdie vlak. Daar is bevind dat die oksidatiewe addisie van HCN aan die voorgangerkompleks (etileen)-NiL2 (L=PH3) in een stap kan plaasvind en in die gasfase snelheidsbepalend is. Die adduk (ettileen)NiHCNL2 bevat H+ (wat ‘n hidried word) en CN- in die cis-posisie relatief tot mekaar. Liganddissosiasie lewer drie isomere van (etileen)NiHCNL. Daar is bevind dat slegs twee van dié isomere aan die katalitiese reaksie kan deelneem, omdat die migrasie-inplasing (migration-insertion) van etileen in die Ni-H-binding voor, of saam met, die assosiasie van ‘n tweede etileen-molekule plaasvind. Dit is slegs moontlik indien waterstof en etileen cis teenoor mekaar is, wat geld vir twee van die isomere. Die meganisme van assosiatiewe reduktiewe eliminasie word deur die berekeninge gerugsteun. Voorts blyk dit vanuit die berekeninge dat die etiel- en sianiedgroepe cis teenoor mekaar moet wees voordat reduktiewe eliminasie van propionitriel kan plaasvind. Analise van die energetiese profiel van die reaksie toon dat entropie-effekte ‘n belangrike rol speel in die voortsetting van die reaksie in die gasfase. Die invloed van Lewissure op die katalitiese siklus word, met behulp van strukturele en energetiese analise bespreek. ‘n Belangrike algemene gevolgtrekking is dat die standaardvoorstelling van die energetiese profiel van reaksies waarin intermolekulêre oorgange (teenoor slegs intramolekulêre oorgange) voorkom, misleidend kan wees. Dit word gestel dat die implisiete aanname dat twee spesies wat minumum-energiestrukture verteenwoordig op twee verskillende potensiële energie-oppervlaktes ook ‘n minimum-energiestruktuur voorstel op een potensiële energie-oppervlakte, die energieprofiel skeeftrek. Gevolgtrekkings vanuit hierdie energieprofiele van reaksies waar meer as een onderskeibare spesie deelneem, moet dus met omsigtigheid gemaak word.

Thesis (PhD)--Stellenbosch University, 2014. / ENGLISH ABSTRACT: see full text for abstract. / AFRIKAANSE OPSOMMING: Sien volteks vir die opsomming.

Thesis (MSc)--Stellenbosch University, 2000. / ENGLISH ABSTRACT: Please refer to fulltext for abstract / AFRIKAANSE OPSOMMING: Sien asb opsomming vir volteks

Thesis (MSc)--Stellenbosch University, 2001. / ENGLISH ABSTRACT: Please refer to fulltext for abstract / AFRIKAANSE OPSOMMING: Sien volteks vir opsomming

Thesis (MSc)--Stellenbosch University, 2003. / ENGLISH ABSTRACT: Modification of chitosan with benzoylisothiocyanate was attempted, however due to solvent problem the study was left incomplete till appropriate solvent is designed. N,N-diethyl-N -camphanoylthiourea (HL8), N-piperidyl-N '-camphanoylthiourea (HL9), N-pyrrolidyl-N -camphanoylthiourea (HL10) and N,N-diethyl-N -adamantylcarbonyl thiourea (HL11)have been synthesised and characterised for the first time. Two of these ligands HL8 and HL11, were used to form a number of transition metal complexes, namely H30+{fae-[Co(L8-S,Obn, cis-[Ni(L8-S,0)2], trans-[Cu(L8-S,0)2], translcis-[Zn(L 8_S,0)2], translcis-[Pt(L 8_S,0)2], Ag2[(HL8-S)(L-J.1-S,O)]2, translcis- [Ni(L11-S,O)2]and translcis-[Cu(L11_S,O)2]. The new products are fully characterised by means of MS, IR spectroscopy, NMR spectroscopy, elemental (C, H, Nand S) analysis and melting point determinations. The H30+{fae-[Co(L8-S,Obn, cis-[Ni(L8- S,O)2], trans-[Cu(L8-S,O)2] and Ag2[(HL8-S)(L-J.1-S,O)]2 are also characterised by Xray diffraction analysis. The structure of the new chiral N,N-dialkyl-N' -camphanoylthiourea ligand (HL8) has a significant effect on its coordination chemistry with transition metal ions. This ligand forms H30+ {fae-[Co(L8-S,Obn, cis-[Ni(L8-S,0)2], trans-[Cu(L-S,O)2] and Ag2[(HL8- S)(L8-J.1-S,O)]2 complexes with the Co(II), Ni(II), Cu(II) and Ag(I) metal ions respectively. The spectroscopic and X-ray diffraction results of these complexes indicate a bidentate mode of coordination of the ligand (with its Sand °donor atoms) to the Co(II), Ni(II) and Cu(II) metal ions. The reaction of this ligand with silver(I) however affords the formation of a binuclear silver(I) complex exhibiting monodentate and bidentate modes of coordination within the same complex. The exclusive formation of trans-[Cu(L8-S,0)2] is a new phenomenon for the HL type thiourea ligands with Sand °donor atoms. Up to this point a maximum of 15 % trans-isomer has been reported in ltterature." All the transition metal complexes made with HL8and HL11are air stable in both the liquid and solid states except the H30+{fae-[Co(L 8-S,Ob]} Interestingly the deep green fae- H30+{fae-[Co(L8-S,Obn complex is air sensitive and the Co(II) oxidizes to Co(III) in the complex by atmospheric O2. The oxidation of Co(II) to Co(III) in the complex is confirmed by 1Hand 13CNMR spectra as well as by UV-Visible spectra of the complex. The NMR spectra of the complexes indicated the presence of one isomer in each complex except for the NMR spectra of the platinum complex of the HL8 ligand. The presence of the minor trans-[Pt(L8-S,Q)21 isomer in combination with the major cis-[Pt(L8-S,Q)21 isomer in the platinum complex was indicated by the 1H, 13Cand 195ptNMR spectra of the complex. / AFRIKAANSE OPSOMMING: Pogings om chitosan met benzoylisothiocyanate te modifiseer is onvoltooid gelaat weens die gebrek aan'n geskikte oplosmiddel. N,N-diethyl-N -carnphanoylthiourea (HL8), N-piperidyl-N -camphanoylthiourea (HL9), N-pyrrolidyl-N -camphanoylthlourea (HL10) en N,N-diethyl-N -adamantylcarbonyl thiourea (HL11) is vir die eerste keer gesintetiseer en gekarakteriseer. Twee van die ligande, HL8 en HL11, is gebruik om verskeie oorgangsmetaalkomplekse te berei, nl. H30+{fac-[Co(L8-S,Ohn, cis-[Ni(L8-S,0)2], trans-[Cu(L8-S,0)2], trans/cis-[Zn(L8 - S,0)2], trans/cis-[Pt(L8-S,0)2], Ag2[(HLB-S)(L-jl-S,0)]2, trans/cis-[Ni(L11-S,0)2] en trans/cis-[Cu(L11_S,0)2]. Die nuwe produkte is volledig gekarakteriseer deur middel van MS, IR spektroskopie, KMR spektrometrie, elemente (C, H, N en S) analise en smeltpuntbepaling. Die komplekse H30+{fao-[Co(L8-S,0)3n, cis-[Ni(L8-S,0)2], trans- [Cu(L8-S,0)2] en Ag2[(HLB-S)(L-jl-S,0)]2 is ook deur middel van X-straaldiffraksieanalise gekarakteriseer. Die struktuur van die nuwe chirale N,N-dialkyl-N'-camphanoylthiourea ligand (HL8) het In beduidende invloed op die koordinasie van hierdie ligand met oorgangsmetaalione. Die ligand vorm H30+{fac-[Co(L8-S,Ohn, cis-[Ni(L8-S,0)2], trans-[Cu(L-S,0)2] en Ag2[(HL8-S)(L8-Il-S,0)]2 komplekse met Co(ll)-, Ni(II)-, Cu(II)- en Ag(I)-ione respektiewelik. Spektroskopiese en X-straaldiffraksie-analise van die komplekse toon dat die ligande op 'n bidentate wyse d.m.v. die S- en O-donoratome met Co(II), Ni(lI) en Cu(lI) koordineer. Die reaksie van hierdie ligand met Ag(I)-ione lei egter tot die vorming van 'n dikernige silwer(I)-kompleks waarin die ligande monodentaat (S) en bidentaat (S en 0) aan die metaal gebind is. Die vorming van uitsluitlik die trans-[Cu(L8-S,0)2] in die reaksie van HL8 met Cu(lI) is 'n besondere fenomeen in die chemie van hierdie tipe ligande; in die literatuur word melding gemaak van slegs een ander trans-kompleks met hierdie ligande, en dan wel met 'n maksimum opbrengs van 15%.29 Alle oorgangsmetaalkomplekse met HLB en HL11 is stabiel indien blootgestel aan lug, ongeag of die verbindings opgelos word of in die vastetoestand verkeer, behalwe H30+{fao-[Co(L8-S,Ohn. Die diep-groen gekleurde H30+{fao-[Co(L8-S,Ohn)3]} kompleks is lugsensitief; Co(lI) word deur lugsuurstof na Co(lIl) ge-oksideer. Die oksidasie in die kompleks kan deur middel van 1H en 13CKMR spektrometrie sowel as UV-sigbare spektrofotometrie bevestig word. Die KMR spektra van alle komplekse dui op die teenwoordigheid van slegs een isomeer in oplossing, behalwe in die geval van die platinum(lI) kompleks met HL8. Die teenwoordigheid van lae konsentrasies trans-[Pt(L8-S,0)2] isomeer tesame met veel hoër konsentrasies van die cis-[Pt(L8 -S,O)2] isomeer word deur 1H, 13Cen 195ptKMR spektroskopie aangedui.

published_or_final_version / abstract / Chemistry / Doctoral / Doctor of Philosophy