Metathesis is a valuable reaction for the production of new alkenes. In the last 50 years, heterogeneous as well as homogeneous catalysts have been used for this reaction. In the homogeneous category are the very successful catalysts designed by the Grubbs group. The first generation Grubbs precatalyst (Gr1) bearing two phosphine ligands was followed after extensive studies by the more active second generation Grubbs precatalyst (Gr2). In Gr2, one of the phosphine ligands is replaced with an N-heterocyclic carbene. Grubbs type precatalysts bearing pyridynyl-alcoholato chelating ligands are pertinent to this study. Scheme 1: The synthesis of Grubbs type precatalysts bearing a pyridynyl-alcoholato ligand. In two previous studies, both supported by computational methods, Grubbs type precatalysts with N^O chelating ligands were synthesised. These investigations were motivated by the fact that chelating ligands bearing different donor atoms can display hemilability. The loosely bound donor atom can de-coordinate to make available a coordination site to an incoming substrate “on demand”, whilst occupying the site otherwise and hence preventing decomposition via open coordination sites. In the first investigation, the incorporation of an O,N-ligand with both R1 and R2 being phenyl groups into the Gr2 precatalyst, resulted in an increase in activity, selectivity and lifetime of the precatalyst in comparison to Gr2 in the metathesis reaction with 1- octene. In the second study, three synthesised complexes were found to be active for the metathesis of 1-octene. This computational study sought to better understand the structural differences and thermodynamic properties of these Grubbs type precatalysts with bidentate/hemilabile ligands. A large number of structures were constructed in Materials Studio by varying the R groups of the bidentate/hemilabile ligand attached to both the Gr1 and Gr2 catalysts. The majority of structures were Gr1-type complexes. For each ligand selected, a group of structures consisting of closed precatalyst, open precatalyst, and where applicable a precatalyst less PCy3, closed metallacycle, open metallacycle and where applicable a metallacycle less PCy3, was constructed and optimised using DMol3. Bond lengths, bond angles, HOMO and LUMO energies and Hirshveld charges of structures were compared with one another. PES scans were performed on the metallacycles of four groups. The purpose of the PES scans was to ascertain whether these bidentate ligands were hemilabile and to illuminate the preferred reaction mechanism for these types of precatalysts. The major finding of this study was that the possibility of an associative mechanism cannot be ruled out for some Gr2-type precatalysts with bidentate ligand. For some precatalysts hemilability is energetically expensive and possibly not viable. No evidence of a concerted mechanism was found. The dissociative mechanism was found to be the preferred mechanism for most of the structures that were subjected to PES scans. The HOMO-LUMO energies of a complex can be used, as a predictive tool, to assess the reactivity and stability of a complex, as well as its preference for substrates. / Thesis (MSc (Chemistry))--North-West University, Potchefstroom Campus, 2013.

Metathesis is a valuable reaction for the production of new alkenes. In the last 50 years, heterogeneous as well as homogeneous catalysts have been used for this reaction. In the homogeneous category are the very successful catalysts designed by the Grubbs group. The first generation Grubbs precatalyst (Gr1) bearing two phosphine ligands was followed after extensive studies by the more active second generation Grubbs precatalyst (Gr2). In Gr2, one of the phosphine ligands is replaced with an N-heterocyclic carbene. Grubbs type precatalysts bearing pyridynyl-alcoholato chelating ligands are pertinent to this study. Scheme 1: The synthesis of Grubbs type precatalysts bearing a pyridynyl-alcoholato ligand. In two previous studies, both supported by computational methods, Grubbs type precatalysts with N^O chelating ligands were synthesised. These investigations were motivated by the fact that chelating ligands bearing different donor atoms can display hemilability. The loosely bound donor atom can de-coordinate to make available a coordination site to an incoming substrate “on demand”, whilst occupying the site otherwise and hence preventing decomposition via open coordination sites. In the first investigation, the incorporation of an O,N-ligand with both R1 and R2 being phenyl groups into the Gr2 precatalyst, resulted in an increase in activity, selectivity and lifetime of the precatalyst in comparison to Gr2 in the metathesis reaction with 1- octene. In the second study, three synthesised complexes were found to be active for the metathesis of 1-octene. This computational study sought to better understand the structural differences and thermodynamic properties of these Grubbs type precatalysts with bidentate/hemilabile ligands. A large number of structures were constructed in Materials Studio by varying the R groups of the bidentate/hemilabile ligand attached to both the Gr1 and Gr2 catalysts. The majority of structures were Gr1-type complexes. For each ligand selected, a group of structures consisting of closed precatalyst, open precatalyst, and where applicable a precatalyst less PCy3, closed metallacycle, open metallacycle and where applicable a metallacycle less PCy3, was constructed and optimised using DMol3. Bond lengths, bond angles, HOMO and LUMO energies and Hirshveld charges of structures were compared with one another. PES scans were performed on the metallacycles of four groups. The purpose of the PES scans was to ascertain whether these bidentate ligands were hemilabile and to illuminate the preferred reaction mechanism for these types of precatalysts. The major finding of this study was that the possibility of an associative mechanism cannot be ruled out for some Gr2-type precatalysts with bidentate ligand. For some precatalysts hemilability is energetically expensive and possibly not viable. No evidence of a concerted mechanism was found. The dissociative mechanism was found to be the preferred mechanism for most of the structures that were subjected to PES scans. The HOMO-LUMO energies of a complex can be used, as a predictive tool, to assess the reactivity and stability of a complex, as well as its preference for substrates. / Thesis (MSc (Chemistry))--North-West University, Potchefstroom Campus, 2013.

The well-defined ruthenium-carbene complexes reported by Grubbs and co-workers were the first ruthenium catalysts to show good activity and selectivity in metathesis of acyclic and cyclic olefins. Unfortunately the use of the Grubbs type catalysts is limited to the small scale synthesis of polymers and essential organic reactions, due to cost and instability of the catalyst at elevated temperatures. Some of the most successful Grubbs-type catalysts included hemilabile ligands. By releasing a free coordination site (the so-called "on-demand-open-site") for an incoming nucleophile, hemilabile ligands have the ability to increase the thermal stability and activity of a catalytic system, by stabilization of the transition metal centre. Previous studies indicated that the incorporation of a sterically hindered N and 0 chelating ligand increased the stability, activity and selectivity of Grubbs type complexes and increasing the electron density of the complex can influence the stability of a complex and therefore the catalytic performance. In this study alicyclic, bidentate N and 0 chelating ligands (16-19) were modelled in order to evaluate the hemilability of these ligands. The modelling was used as a comer stone from which the synthesis was conducted. Molecular modelling showed that of the four ligands identified only two (16 and 18) could potentially be hemilabile. 17 would rather form a transaunular ether compound. The modelling results were incondusive for ligand 19 and further investigation is necessary for this compound… / Thesis (M.Sc. (Chemistry))--North-West University, Potchefstroom Campus, 2010.

The well-defined ruthenium-carbene complexes reported by Grubbs and co-workers were the first ruthenium catalysts to show good activity and selectivity in metathesis of acyclic and cyclic olefins. Unfortunately the use of the Grubbs type catalysts is limited to the small scale synthesis of polymers and essential organic reactions, due to cost and instability of the catalyst at elevated temperatures. Some of the most successful Grubbs-type catalysts included hemilabile ligands. By releasing a free coordination site (the so-called "on-demand-open-site") for an incoming nucleophile, hemilabile ligands have the ability to increase the thermal stability and activity of a catalytic system, by stabilization of the transition metal centre. Previous studies indicated that the incorporation of a sterically hindered N and 0 chelating ligand increased the stability, activity and selectivity of Grubbs type complexes and increasing the electron density of the complex can influence the stability of a complex and therefore the catalytic performance. In this study alicyclic, bidentate N and 0 chelating ligands (16-19) were modelled in order to evaluate the hemilability of these ligands. The modelling was used as a comer stone from which the synthesis was conducted. Molecular modelling showed that of the four ligands identified only two (16 and 18) could potentially be hemilabile. 17 would rather form a transaunular ether compound. The modelling results were incondusive for ligand 19 and further investigation is necessary for this compound… / Thesis (M.Sc. (Chemistry))--North-West University, Potchefstroom Campus, 2010.

Ring closing metathesis (RCM) is a chemical transformation that converts a bisalkene compound into a cycloalkene. It is catalyzed by transition metal complexes containing carbene ligands (that feature metal-carbon double bonds). The mechanism is well-understood, however, there are numerous details of the reaction that are less well understood, especially concerning catalyst activation and decomposition and formation of byproducts. This thesis takes a new approach to the study of RCM: analysis of the reaction using real-time mass spectrometric techniques. Electrospray ionization (ESI) mass spectrometry was employed in this study, and the real-time aspect was enabled by using pressurized sample infusion (PSI). Observation of the reactants and products was enabled using charge-tagged bis-alkenes of the general formula [Bu2N{(CH2)nCH=CH2}2]+ [PF6]–. These were synthesized in two steps using a generally applicable methodology to generate a wide range of ring sizes of the product, from 5- to 15-membered rings. Examination of their behavior under carefully optimized RCM conditions using Grubbs’ second-generation catalyst showed a wide variation in reaction rates and amount of byproducts, largely due to ring-strain effects (especially high for 5- and 9-membered rings). Byproducts always exhibited a 14 Da mass unit difference from starting materials or products, and Orbitrap MS analysis confirmed it was CH2. Isomerization was suspected to lead to byproducts. A pathway for byproducts via isomerization and cross metathesis was proposed. The source of actual isomerization catalyst was believed to be from the precatalyst itself as the evidence of precatalyst decomposition was observed. Finally, to prove our isomerization hypothesis, an authentic isomerization catalyst was deliberately added into a fast and clean reaction along with Grubbs’ second-generation catalyst, and it produced the expected byproducts. Only small amounts of oligomeric intermediates were observed, probably because of the low concentrations used. [ClPCy3]+ was a new short-lived decomposition product stemming from catalyst breakdown, along with already-known imidazolium and protonated phosphine decomposition products. Overall, the thesis provides deep new insights into the nature of RCM reactions, in particular revealing the importance of isomerization in RCM reactions that are slow due to ring strain effects and in uncovering a new decomposition pathway for important RCM catalysts. / Graduate

In this study, we were particularly interested in looking at the possibility that cross metathesis of olefins in melt phase could be used to produce polydimethylsiloxane (PDMS) modified polypropylene (PP). The intention of this project was also to study and quantify relationships among the main experimental factors in the reaction: temperature, catalyst concentration and molar ratio of PP to PDMS, through a 2-level factorial statistical design. In order to examine if PP-PDMS copolymers were synthesized in the melt phase, measurement of the chemical, physical and viscoelastic properties of the synthesized copolymers was necessary. Techniques including proton (¹H)-nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), rheometry and scanning electron microscopy (SEM), were all used to characterize the synthesized copolymers. ¹H NMR measurements confirmed the presence of PDMS in the copolymers. They also provided a quantitative measurement of PP to PDMS molar ratio in copolymers by determining the integration of PP PDMS repeating unit signals in NMR spectra. Compared to virgin PP, a lower melting enthalpy of the PP phase in the copolymer was observed from DSC results. This implied that the PDMS component influenced the thermal behavior of the PP crystalline phase in the copolymers. Moreover, TGA measurements indicated that a higher thermal stability was obtained for PP-PDMS copolymers than that for virgin PP wax and this was expected since PDMS is known for its excellent stability at high temperature. Rheological analysis showed that the presence of PDMS in the copolymers gave lower complex viscosities and loss moduli, but higher storage moduli than those for virgin PP. Furthermore, the morphology of copolymers was examined by SEM and elemental analysis at the surface using an energy dispersive X-ray (EDX) analyzer on the SEM. It was found that micrographs of copolymers showed round domains on the surface, which were not observed in virgin PP wax and those round segments were confirmed to contain silicon. Torque values used in a batch mixer for polymerizations and the remaining weight % of copolymers at 350°C were used to conduct statistical analysis, through which models used to describe the relationships between experimental factors and these physical responses were determined.

In this study, we were particularly interested in looking at the possibility that cross metathesis of olefins in melt phase could be used to produce polydimethylsiloxane (PDMS) modified polypropylene (PP). The intention of this project was also to study and quantify relationships among the main experimental factors in the reaction: temperature, catalyst concentration and molar ratio of PP to PDMS, through a 2-level factorial statistical design. In order to examine if PP-PDMS copolymers were synthesized in the melt phase, measurement of the chemical, physical and viscoelastic properties of the synthesized copolymers was necessary. Techniques including proton (¹H)-nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), rheometry and scanning electron microscopy (SEM), were all used to characterize the synthesized copolymers. ¹H NMR measurements confirmed the presence of PDMS in the copolymers. They also provided a quantitative measurement of PP to PDMS molar ratio in copolymers by determining the integration of PP PDMS repeating unit signals in NMR spectra. Compared to virgin PP, a lower melting enthalpy of the PP phase in the copolymer was observed from DSC results. This implied that the PDMS component influenced the thermal behavior of the PP crystalline phase in the copolymers. Moreover, TGA measurements indicated that a higher thermal stability was obtained for PP-PDMS copolymers than that for virgin PP wax and this was expected since PDMS is known for its excellent stability at high temperature. Rheological analysis showed that the presence of PDMS in the copolymers gave lower complex viscosities and loss moduli, but higher storage moduli than those for virgin PP. Furthermore, the morphology of copolymers was examined by SEM and elemental analysis at the surface using an energy dispersive X-ray (EDX) analyzer on the SEM. It was found that micrographs of copolymers showed round domains on the surface, which were not observed in virgin PP wax and those round segments were confirmed to contain silicon. Torque values used in a batch mixer for polymerizations and the remaining weight % of copolymers at 350°C were used to conduct statistical analysis, through which models used to describe the relationships between experimental factors and these physical responses were determined.

There are two sections to this research dissertation. Part one includes syntheses of fused-ring heterocycles derived from thiazole, oxazole, benzoxazole and benzothiazole derivatives and trifluoroacetylations of in situ generated N-methyl cyclic ketene-N,O/Sacetals. Attempted functionalized polymer syntheses from plant-derived 5-(hydroxymethyl) furfural are discussed in part two. Three 2-methylthiazoles, 2,4,5-trimethyloxazole, 2-methylbenzoxazole and 2- methyl-benzothiazole were each reacted with benzoyl chloride in acetonitrile/triethylamine to generate benzyl-vinyl esters. Base hydrolysis of these benzyl-vinyl esters formed 2-(heterocyclic)-1-phenylethenols which exist in both ketoenol tautomeric forms. These tautomers were used as starting materials for fused-ring heterocycle syntheses. Each tautomeric pair react with dimethyl acetylenedicarboxylate in methanol giving the 5,6-ringused 8-benzoyl-5-oxo-5H-thiazolo-, 8-benzoyl-5-oxo-5H-oxazolo-, 4-benzoyl-1-oxo-1H-benzo[4,5]oxazolo- and 4-benzoyl-1-oxo-1H-benzo[4,5]thiazolo [3,2-a]pyridinecarboxylate derivatives. Two novel 5,7-ringused 9-benzoyl-2,3- dimethyl-5,6-dihydrothiazolo- and 9-benzoyl-2,3-dimethyl-5,6-dihydrooxazolo[3,2-a] azepine-5,6,7,8-tetracarboxylates formed when the tautomers formed from 2,4,5- trimethyl thiazole and 2,4,5-trimethyl oxazole were reacted with DMADC. These tautomers react with 1,3-diacid chlorides in acetonitrile/triethylamine affording the 5,6-ringused 8-benzoyl-6,6-dialkyl-6H-thiazolo- and 8-benzoyl-6,6- dimethy-6H-oxazolo-, 4-benzoyl-2,2-dimethyl-1H-benzo[4,5]thiazolo- and 4-benzoyl- 2,2-dimethyl-1H-benzo[4,5]oxazolo[3,2,-a]pyridinedione derivatives. Functionalized 5,6- ringused 8-benzoyl-6H-thiazolo- and 8-benzoyl-6H-oxazolo[3,2]pyrimidine-5,7- diones, and 4-benzoyl-1H-benzo[4,5]thiazolo- and 4-benzoyl-1H-benzo[4,5]oxazolo[3,2- c]pyrimidine-1,3(2H)-diones formed reacting the tautomers with N-chlorocarbonyl isocyanate in THF/triethylamine. Significant ring size and substituent effects were observed in trifluoroacetylations of in situ-generated cyclic ketene-N,O/S acetals. In situ-generated 3,4,4-trimethyl-2- methylene-oxazolidine, 3-methyl-2-methylene-oxazolidine and 3-methyl-2-methylene- 1,3-oxazinane each formed β,β-bistrifluoroacetylated products. However, 3-methyl-2- methylene-oxazolidine also afforded a γ-lactam by an iodide-catalyzed rearrangement of its β,β-bistrifluoroacetylated derivative. In situ-generated 3-methyl-2-methylenethiazolidine gave both β-mono- and β,β-bistrifluoroacetylation products. 5-(Hydroxymethyl)furfural synthesized from sucrose was converted to 2,5- bis(hydroxymethyl)furan (2,5-BHMF). 7-Oxanorbornene-type Diels-Alder adducts synthesized from 2,5-BHMF were used as monomers for both ring opening metathesis polymerizations (ROMPs) and polycondensations. ROMP, followed by polycondensation or vise versa were expected to give highly functionalized cross-linked polymers. ROMP of the monomers using three Grubbs’ 1st, 2nd and 3rd generation catalysts were unsuccessful due to the presence of hydroxymethyl groups at one or both bridgeheads that could coordinate Ruthenium. With one bridgehead methyl present ROMP proceeded. Low molecular weight polyesters were synthesized via polycondensation. One was crosslinked using ROMP, but not to its gel point.

L'un des objectifs principaux de l'imagerie par résonance magnétique fonctionnelle (IRMf) est la localisation in vivo et de manière non invasive des zones cérébrales associées à certaines fonctions cognitives. Le cerveau présentant une très grande variabilité anatomo-fonctionnelle inter-individuelle, les études d'IRMf incluent généralement plusieurs sujets et une analyse de groupe permet de résumer les résultats intra-sujets en une carte d'activation du groupe représentative de la population d'intérêt. L'analyse de groupe « standard » repose sur une hypothèse forte d'homogénéité des effets estimés à travers les sujets. Dans un premier temps, nous étudions la validité de cette hypothèse par une méthode multivariée diagnostique et un test de normalité univarié (le test de Grubbs). L'application de ces méthodes sur une vingtaine de jeux de données révèle la présence fréquente de données atypiques qui peuvent invalider l'hypothèse d'homogénéité. Nous proposons alors d'utiliser des statistiques de décision robustes calibrées par permutations afin d'améliorer la spécificité et la sensibilité des tests statistiques pour l'analyse de groupe. Puis nous introduisons de nouvelles statistiques de décision à effets mixtes fondées sur le rapport de vraisemblances maximales, permettant de pondérer les sujets en fonction de l'incertitude sur l'estimation de leurs effets. Nous confirmons sur des jeux de données que ces nouvelles méthodes d'inférence permettent un gain en sensibilité significatif, et nous fournissons l'ensemble des outils développés lors de cette thèse à la communauté de neuro-imagerie dans le logiciel DISTANCE.

The thesis is focused on setting land prices according to the rules of valuation and market price (the current). Selected lands are placed in non-structural locations and locations designed to be constructed at selected stages of landscape planning. Based on gained results was made evaluation of how various stages of landscape planning affects the current price and also the administrative price. The thesis also explains the cause of the difference and way how it affects the price of invested land.