Ph.D. / Compounds, 2,6-bis(3,5-dimethylpyrazol-1-ylmethyl)pyridine (L1) and 2,6-bis(3,5-ditertbutylpyrazol-1-ylmethyl)pyridine (L2) were prepared by phase transfer alkylation of 2,6-bis(bromomethyl)pyridine with two mole equivalents of the appropriate pyrazole. Ligands L1 and L2 reacted with either [PdCl2(NCMe)2] or [PdClMe(COD)] to form mononuclear palladium complexes [(PdCl2(L1)] (1), [(PdClMe(L1)] (2), [(PdCl2(L2)] (3), [(PdClMe(L2)] (4). All new compounds prepared were characterised by a combination of 1H NMR, 13C NMR spectroscopy and microanalyses. The coordination of L2 in a bidentate fashion through the pyridine nitrogen atom and one pyrazolyl nitrogen atom has been confirmed by single crystal X-ray crystallography of complex 3. Reactions of 1, 2 and 3 with the halide abstractor NaBAr4 (Ar = 3,5-(CF3)2C6H3) led to the formation of the stable tridentate cationic species [(PdCl(L1)]BAr4 (5), [(PdMe(L1)]BAr4 (6) and [(PdCl(L2)]BAr4 (7) respectively. Tridentate coordination of L1 and L2 in the cationic complexes has also been confirmed by single X-ray crystallography of complexes 5 and 6. The analogous carbonyl linker cationic species, [Pd{(3,5-Me2pz-CO)2-py}Cl]+ (9) and [Pd{(3,5-tBu2pz-CO)2-py}Cl]+ (10), prepared by halide abstraction from [Pd{(3,5-Me2pz-CO)2-py}Cl2] and [Pd{(3,5-tBu2pz-CO)2-py}Cl2] with NaBAr4, were however less stable. While cationic complexes 5-7 showed indefinite stability in solution, 9 and 10 had t1/2 of 14 and 2 days respectively. Attempts to crystallise 1 and 3 from the mother liquor resulted in the isolation of the salts [PdCl(L1)]2[Pd2Cl6] (11) and [PdCl(L2)]2[Pd2Cl6] (12). Although when complexes 1-4 xviii were reacted with modified methylaluminoxane (MMAO) or NaBAr4, no active catalysts for ethylene oligomerisation or polymerisation were formed, activation with silver triflate (AgOTf) produced active catalysts that oligomerised and polymerised phenylacetylene to a mixture of cis-transoidal and trans-cisoidal polyphenylacetylene. Compounds 2-(3,5-dimethylpyrazol-1-ylmethyl)pyridine (L3) and 2-(3,5-di-tert-butylpyrazol-1-ylmethyl)pyridine (L4) were prepared by phase transfer alkylation of 2-picolylchloride hydrochloride with one mole equivalent of the appropriate pyrazole. Compounds 2-(3,5-bis-trifluoromethyl-pyrazol-1-ylmethyl)-6-(3,5-dimethyl-pyrazol-1-ylmethyl)-pyridine (L5) and 2-(3,5-dimethyl-pyrazol-1-ylmethyl)-6-phenoxymethyl-pyridine (L6) were isolated in good yields by reacting (2-chloromethyl-6-3,5-dimethylpyrazol-1-ylmethyl)pyridine with an equivalent amount of potassium salt of 3,5-bis(trifluoromethyl)pyrazolate and potassium phenolate respectively. L3-L6 react with either [Pd(NCMe)2Cl2] or [PdClMe(COD)] to give mononuclear palladium complexes 13-18 of the general formulae [PdCl2(L)] or [PdClMe(L)] where L = is the bidentate ligands L3, L4, L5 and L6 respectively. Single crystal X-ray crystallography of complexes 13, 15 and 16 has been used to confirm the solid state geometry of the complexes. In attempts to generate active olefin oligomerisation catalysts, the chloromethyl Pd(II) complexes 14 and 16 were reacted with the halide abstractor NaBAr4 in the presence of stabilising solvents (i.e Et2O or NCMe) but no catalytic activities were observed. Decomposition was evident as observed from the deposition of palladium black in experiments using Et2O. In experiments where NCMe was used as the stabilising solvent, the formation of cationic species stabilised by NCMe was evident from 1H NMR analyses. Reaction of complex 14 with NaBAr4 on a preparative scale in a mixture of CH2Cl2 and NCMe solvent gave the cationic complex [[PdMeNCMe(L3)]BAr4 (19) in good yields. Complex 17 reacted with NABAr4 to give tridentate cationic species [[PdMe(L5)]BAr4 (20) which is inactive towards ethylene oligomerisation or polymerisation reactions. The tridentate coordination of L5 in 20 has also been established by single crystal X-ray structure of 20. Catalysts generated from 18 and 19 catalysed ethylene polymerisation at high pressures to branched polyethylene; albeit with very low activity. The Choromethyl palladium complex 14 reacted with sulfur dioxide to form complex 21. The nature of the product has been established by 1H NMR, 13C NMR and mass spectrometry to be an insertion product of SO2 into the Pd-Me bond of 14. Compounds L1-L4 reacted with the nickel salts NiCl2 or NiBr2 in a 1:1 mole ratio to give the nickel complexes [NiCl2(L1)] (22), [NiBr2(L1)] (23), [NiCl2(L2)] (24), and [NiBr2(L2)] (25), [Ni2(μ2-Cl)2Cl2(L3)2] (26), [Ni2(μ2-Br)2Br2(L3)2] (27), [NiCl2(L4)] (29) and [NiBr2(L4)] (30) in good yields. Reaction of L3 with NiBr2 in a 2:1 mole gave the octahedral complex [NiBr2(L4)2] (28) in good yields. Complexes 22-30 were characterised by a combination micro-analyses, mass spectrometry and single crystal X-ray analyses for 27 and 30. No NMR data were acquired because of the paramagnetic nature of the complexes. When complexes 22-30 were activated with EtAlCl2, highly active olefin oligomerisation catalysts were formed. In the ethylene oligomeristion reactions, three oligomers: C11, C14 xx and C16 were identified as the major products. Selectivityof 40% towards α-olefins were generally obtained. In general catalysts that contain the bidentate ligands L3 and L4 were more active than those that contain the tridentate ligands L1 and L2. Dichloride complexes exhibited relatively higher catalytic activities than their dibromide analogues. Turn over numbers (TON) for oligomer formation showed high dependence on ethylene concentration. A Lineweaver-Burk analysis of reactions catalysed by 22 and 26 showed TON saturation of 28 393 kg oligomer/mol Ni.h and 19 000 kg oligomer/mol Ni.h respectively. Catalysts generated from complexes 22-30 also catalysed oligomerisation of the higher olefins, 1-pentene, 1-hexene and 1-heptene and displayed good catalytic activities. Only two products C12 and C15 were obtained in the 1-pentene oligomerisation reactions. The 1-hexene reactions also gave two products, C12 and C18, while 1-heptene oligomerisation reactions gave predominantly C14 oligomers. Five benzoazoles were used to prepare a series of palladium complexes that were invesitigated as Heck coupling catalysts. The compounds 2-pyridin-2-yl-1H-benzoimidazole (L7) and 2-pyridin-2-yl-benzothiazole (L8) were prepared following literature procedures. The new ligands 2-(4-tert-butylpyridin-2-yl)-benzooxazole (L9) and 2-(4-tert-butyl-pyridin-2-yl)-benzothiazole (L10) were prepared by ring closure of aminophenol and aminothiophenol with tert-butyl picolinic acid respectively. The ligand 6-tert-Butyl-2-(4-tert-butyl-pyridin-2-yl)-benzothiazole (L11) was prepared by intramolecular cyclisation under basic conditions is described. Reactions of L7-L11 with either [Pd(NCMe)2Cl2] or [Pd(COD)MeCl] afforded the corresponding mononuclear palladium complexes [PdClMe(L7)] (31), [PdClMe(L8)] (32), [PdCl2(L9)] (33), [PdMeCl(L9)] (34), [PdCl2(L10)] (5), [PdMeCl(L10)] (36) and [PdMeCl(L11)] (37) as xxi confirmed by mass spectrometry and micro-analyses. The palladium complexes 31-37 were efficient Heck coupling catalysts for the reaction of iodobenzene with butylacrylate under mild conditions and showed good stability.

M.Sc. (Chemistry) / This study deals with the synthesis of nitrogen-donor pyrazole- and pyrazolylethylamine compounds, their reactions with palladium(II) and nickel(II) precursors to form complexes and the applications of theses palladium(II) and nickel(II) complexes as catalysts for ethylene oligomerization reactions and reactions of higher α-olefins in Friedel-Crafts alkylation of aromatic solvents. A series of ligands, 3,5-di-tert-butyl-1H-pyrazole (L3), 3,5-diphenyl-1H-pyrazole (L4), 5-phenyl-3-(trifluoromethyl)-1H-pyrazole (L5) were synthesized using appropriate amounts of diketones and hydrazine hydrate; while ligands, 2-(1H-pyrazol-1-yl)ethylamine (L6), 2-(3,5-dimethyl-1H-pyrazol-1-yl)-ethylamine (L7), 2-(3,5-di-tert-butyl-1H-pyrazol-1-yl)-ethylamine (L8), 2-(3,5-diphenyl-1H-pyrazol-1-yl)-ethylamine (L9) and 2-(5-phenyl-3-(trifluoromethyl)-1H-pyrazol-1-yl)ethylamine (L10) were prepared via the N sp3 alkylation of the corresponding pyrazoles with bromoethylamine Reactions of L1-L5 with [PdCl2(CNMe)2] formed five complexes of general formula [PdCl2 (L)2] {L = L1 (2.1), L2 (2.2), L3 (2.3), L4 (2.4) and L5 (2.5)}. Similarly [NiBr2(DME)] formed five complexes of general formula [NiBr2(L)2] {L = L1(2.6), L2 (2.7), L3 (2.8), L4 (2.9) and L5 (2.10)}. Complexes 2.1-2.10 were synthesized in a 2:1 mole ratio of ligand and metal precursor. Reactions of L6-L10 with [PdCl2(MeCN)2] yielded complexes 3.1-3.5 respectively. Ligands L6-L10 were also complexed with NiCl2.6H2O to give complex 3.6 while [NiCl2(DME)] and [NiBr2(DME)] gave complexes 3.7-3.8 and 3.9-3.13 respectively...

M.Sc. / In search of developing new pyrazolyl complexes that can be used for ethylene transformation reactions, bis(pyrazolyl)alky carbonyl and amine complexes were prepared. The reaction between 3,5-dimethylpyrazole with alkyl-carbonyl chloride linkers in the presence of triethylamine as a base produced the ligands, 1,3-bis(3,5- dimethylpyrazol-1-yl)-propan-1-one (L1), 1,2-bis(3,5-dimethylpyrazol-1-yl)-ethane- 1,2-dione (L2), 1,4-bis(3,5-dimethylpyrazol-1-yl)-butane-1,4-dione (L3) and 1,6- bis(3,5-dimethylpyrazol-1-yl)-hexane-1,6-dione (L4) as white to brown crystalline solids in good yields. Ligand L5 was prepared by using bis(2-chloroethyl)-amine hydrochloride and 3,5- dimethylpyrazolevia via a phase-transfer reaction, while L6 was obtained using the bis(2-chloroethyl)-amine hydrochloride and 3,5-diphenypyrazole in the presence of triethylamine as a base. They were isolated in moderate yields, while their ditertiarypyrazole derivative was not obtained at all. All the ligands were characterized by a combination of 1H and 13C{1H}-NMR spectroscopy, infrared spectroscopy, elemental analysis and mass spectrometry. Ligands L1 and L4 were further confirmed by X-ray crystallography. Ligands L1 and L6 were subsequently used to prepare their corresponding Pd, Ni and Cr complexes. L1 was reacted with [PdCl2(NCMe)2] to form a bidentate complex 1,3- bis-(3,5-dimethylpyrazol-1-yl)-propan-1-one palladium dichloride (1a) when the reaction was heated at 80 oC, while a tridentate complex 1,3-bis(3,5-dimethylpyrazol- 1-yl)-propan-1-one palladium chloride (1b) was obtained when the reaction was refluxed. 1,3-bis(3,5-dimethylpyrazol-1-yl)-propan-1-one nickel(II) bromide (2) was obtained when NiBr2 was reacted with L1 at room temperature while the reaction between L1 and [CrCl3(THF)3] gave 1,3-bis(3,5-dimethylpyrazol-1-yl)-propan-1-one chromium(III) chloride (3). Ligand L6 was reacted with the same metal salts to give bis[2-(3,5-dimethylpyrazol- 1-yl)-ethyl] amine palladium(II) chloride (4), bis[2-(3,5-dimethylpyrazol-1-yl)-ethyl] amine nickel(II) chloride (5) and bis[2-(3,5-dimethylpyrazol-1-yl)-ethyl] amine chromium(III) chloride (6). All the complexes were characterized by the already mentioned characterization techniques and X-ray analysis was performed for 1b and 4. Ethylene transformation reactions were performed with complexes 1a, 2, 3, 5 and 6, and complexes 1a and 4 were not used because of their geometrical structures, which prevented them to be active for such reactions. Using MMAO and EtAlCl2 as cocatalysts complexes 1a and 3 showed no activity, however complexes 2 and 6 were active. Complex 2 was used with MMAO and showed no activity, while with EtAlCl2 oligomers were produced. Gas-chromatography analysis of the products showed that C6-C14+ oligomers were obtained. Temperature variation reactions performed under standard conditions of 20 bar ethylene pressure and 200 equivalents of EtAlCl2 in one hour showed that certain oligomers were not favoured under certain temperatures. Ethylene reactions with complex 6 and EtAlCl2 did not form any product but with MMAO polymer material was obtained. Analysis of the polymer by differential scanning calometry proved that the product was high density polyethylene. Studies of temperature, co-catalyst and pressure variations were performed. As expected for temperature studies the catalyst decomposed at high temperatures (above 40 oC), while for co-catalyst studies 3000 equivalents of MMAO gave the lowest TON. Pressure variations studies showed that an increase in ethylene pressure also increased the TON, but above 30 bar the activity became stable.

No description available.

M.Sc. / This study describes the synthesis of pyrazolyl palladium and nickel complexes and their applications as catalysts for the co-polymerization of olefins with carbon monoxide and also as ethylene oligomerization catalysts. A series of compounds, 2-(3,5-dimethyl-pyrazol-1-yl)-ethyl]-pyridin-2-ylmethylene-imine (L1), 2-(3,5-di-tert-butyl-pyrazol-1-yl)-ethyl]-pyridin-2-ylmethylene-imine (L2), 2-(3,5-dimethyl-pyrazol-1-yl)-ethyl]-thiophen-2-ylmethylene-imine (L3), 2-(3,5-di-tert-butyl-pyrazol-1-yl)-ethyl]-thiphen-2-ylmethylene-imine (L4), 2-(3,5-dimethyl-pyrazol-1-yl)-ethyl]-5-bromothiophen-2-ylmethylene-imine (L5), 2-(3,5-di-tert-butyl-pyrazol-1-yl)-ethyl]-2bromothiophen-2-ylmethylene-imine (L6), 2-(3,5-dimethyl-pyrazol-1-yl)-ethyl]-pyrrol-2-ylmethylene-imine (L7) and 2-(3,5-di-tert-butyl-pyrazol-1-yl)-ethyl]-pyrrol-2-ylmethylene-imine (L8)] were prepared via Schiff base condensation of the appropriate amines and aldehydes. Reactions of L1-L6 and L8 with [PdClCH3(cod)] formed six complexes of general formula [PdClCH3(L)] {L = L1 (1), L2 (2), L3 (3), L4 (4), L5 (5) and L6 (6)} and [Pd(L8)2] (7). Complexes 1-6 were converted to the cationic compounds [PdCH3(L)]BAr4 {L = L1 (8), L2 (9), L3 (10), L4 (11), L5 (12) and L6 (13)} by the reaction of compounds 1-6 with the halide abstractor Na[BAr4] (where Ar = (3,5-(CF3)2C6H3) in a 1:1 mole ratio. For compounds 8 and 9 the cationic species were stabilized by the coordination of the pyrazolyl units of the ligands, which were uncoordinated in the parent palladium complexes 1 and 2. The cationic complexes 10-13, however, were stabilized by v coordination of NCCH3 to the palladium centre. Complexation of L1, L2, L5 and L6 with [PdCl2(NCCH3)2] gave the palladium dichloro complexes [PdCl2(L)], {L = L1 (14), L2 (15), L5 (16), and L6 (17)}. Compounds L1, L2, L7 and L8 were reduced to form compounds L9-L12 respectively and were reacted with [NiBr2DME] to form complexes [NiBr2(L)] {L = L9 (18), L10 (19), L11 (20) and L12 (21).

Thesis (Ph.D.)--University of Nebraska-Lincoln, 2009. / Title from title screen (site viewed June 26, 2009). PDF text: xxvii, 209 p. : ill. (some col.) ; 17 Mb. UMI publication number: AAT 3350440. Includes bibliographical references. Also available in microfilm and microfiche formats.

No description available.

Silicon-based nanostructures are essential building blocks for nanoelectronic devices and nano-electromechanical systems (NEMS), and their mechanical and electrical properties play an important role in controlling the functionality and reliability of the nano-devices. The objective of this dissertation is twofold: The first is to investigate the mechanical properties of silicon nanolines (SiNLs) with feature size scaled into the tens of nanometer level. And the second is to study the electron transport in nickel silicide formed on the SiNLs. For the first study, a fabrication process was developed to form nanoscale Si lines using an anisotropic wet etching technique. The SiNLs possessed straight and nearly atomically flat sidewalls, almost perfectly rectangular cross sections and highly uniform linewidth at the nanometer scale. To characterize mechanical properties, an atomic force microscope (AFM) based nanoindentation system was employed to investigate three sets of silicon nanolines. The SiNLs had the linewidth ranging from 24 nm to 90 nm, and the aspect ratio (Height/linewidth) from 7 to 18. During indentation, a buckling instability was observed at a critical load, followed by a displacement burst without a load increase, then a fully recoverable deformation upon unloading. For experiments with larger indentation displacements, irrecoverable indentation displacements were observed due to fracture of Si nanolines, with the strain to failure estimated to be from 3.8% to 9.7%. These observations indicated that the buckling behavior of SiNLs depended on the combined effects of load, line geometry, and the friction at contact. This study demonstrated a valuable approach to fabrication of well-defined Si nanoline structures and the application of the nanoindentation method for investigation of their mechanical properties at the nanoscale. For the study of electron transport, a set of nickel monosilicde (NiSi) nanolines with feature size down to 15 nm was fabricated. The linewidth effect on nickel silicide formation has been studied using high-resolution transmission electron microscopy (HRTEM) for microstructural analysis. Four point probe electrical measurements showed that the residual resistivity of the NiSi lines at cryogenic temperature increased with decreasing line width, indicating effect of increased electron sidewall scattering with decreased line width. A mean free path for electron transport at room temperature of 5 nm was deduced, which suggests that nickel silicide can be used without degradation of device performance in nanoscale electronics.

Thesis (M. Sc. Agriculture (Animal Production)) -- University of Limpopo, 2021 / The study was carried out to determine the concentration levels of mercury (Hg), lead (Pb), cadmium (Cd), chromium (Cr), nickel (Ni) and zinc (Zn) in water, soil, witbuffels grass and meat of goats reared along the river banks of Middle Olifants (Mogalatsana village) and Mogalakwena (Papegaai village) rivers. The samples were collected from the river water, soils along the river banks, grass grown along the river banks and male Pedi goats reared in Mogalatsana and Papegaai villages. The samples were analysed for the selected heavy metals with an inductively coupled plasma mass spectroscopy (ICP-MS). Data was analysed as in a complete randomised design. The results of selected heavy metals in water of both rivers ranged from 0.00 mg/litre of water (Ni and Cr) to 0.04 mg/litre of water (Hg). The concentration levels of selected heavy metals in water were similar (P>0.05) for Middle Olifants and Mogalakwena rivers. The concentration levels of selected heavy metals in the soils along the banks of Middle Olifants and Mogalakwena rivers ranged from 0.00 mg/kg DM soil (Hg and Cd) to 63.70 mg/kg DM soil (Cr). There were similar (P>0.05) concentration levels of selected heavy metals in the soils along the banks of Middle Olifants and Mogalakwena rivers. Heavy metal concentration levels in the witbuffels grass grown along the banks of Middle Olifants and Mogalakwena rivers ranged from 0.00 mg/kg DM of grass (Hg and Cd) to 5.05 mg/kg DM of grass (Zn). Similar (P>0.05) concentrations of selected heavy metals were observed in witbuffels grass grown along the banks of Middle Olifants and Mogalakwena rivers. However, the concentration levels of Zn, Pb and Cd in water from both sites were above internationally maximum permissible levels, indicating that the water from these rivers was not safe for drinking by humans and animals. The concentration levels of Ni and Pb in soils from both sites were above internationally recommended maximum permissible limits. Similarly, chromium concentration levels in witbuffels grass from both sites were above the recommended maximum permissible limits for livestock, indicating that the grass was not safe for consumption by livestock. It is recommended that further studies be conducted to ascertain these findings. Blood, liver, kidney and meat samples of yearling male Pedi goats grazing along the banks of Middle Olifants river (Mogalatsana village) had similar (P>0.05) Cr, Cd, Hg, Ni and Pb concentration levels, respectively. However, goat liver samples had higher (P<0.05) Zn concentrations than meat, kidney and blood samples. Samples of goat v meat contained higher (P<0.05) Zn concentrations than those of kidneys and blood. Similarly, goat kidney samples contained more (P<0.05) Zn than blood samples. Blood, liver, kidney and meat samples of Pedi goats grazing along the banks of Mogalakwena river (Papegaai village) contained similar (P>0.05) concentration levels of Cr, Cd, Hg, Ni and Pb, respectively. However, goat meat samples contained higher (P<0.05) Zn concentrations than liver, kidney and blood samples. Samples of goat liver contained higher (P<0.05) Zn concentration levels than kidney and blood samples. Similarly, goat kidney samples contained more (P<0.05) Zn than blood samples. Meat, blood, liver and kidney samples of male Pedi goats raised in Mogalatsana and Papegaai villages had similar (P>0.05) chromium, cadmium, mercury, nickel and lead concentrations, respectively. However, liver and kidney samples of goats from Mogalatsana village had higher (P<0.05) zinc levels than those from Papegaai village. Blood and meat samples of goats from Papegaai village had higher (P<0.05) zinc levels than those from Mogalatsana village. The concentration levels of Zn, Ni, Pb, Cr and Cd in the blood, liver, kidney and meat samples of male Pedi goats reared along the banks of Middle Olifants and Mogalakwena rivers were within the maximum permissible levels for human consumption. Mercury concentration levels in liver, kidney and meat samples of the goats were within the maximum permissible levels for human consumption. However, mercury concentration levels in the blood of goats grazing along the banks of Middle Olifants and Mogalakwena rivers were above the maximum permissible limit of 0.2 mg/litre of blood. It was concluded that meat, livers and kidneys of the goats were fit for human consumption. However, blood from these goats was not fit for human consumption.

No description available.