Magnetic susceptibility studies over the temperature range 87-330°K, on sixteen complexes of copper (11) are reported. The compounds are conveniently divided into two groups. Group I compounds (copper (11) benzoate and its monopyridine adduct, copper (11) meta-chlorobenzoate and its monopyridine and mono-p-dioxane adducts and the monopyridine and hemipyridine adducts of copper (11) para-chlorobenzoate ) possess magnetic properties expected for a binuclear system and values of the exchange integrals have been calculated, for these compounds. The group 11 compounds (the dipyrldlne adducts and the basic salts of copper (ll) benzoate, copper (11) ortho-, meta- and para-chlorobenzoate ) exhibit only weak magnetic interaction --- their magnetic susceptibilities obeying the Curie-Weiss law with small Weiss constants --- and they are considered to have polymeric structures. Copper (11) para-chlorobenzoate exhibits properties intermediate between the group I and 11 compounds. Confirmatory evidence for assigning binuclear structures to the group I compounds has been obtained from the presence, in the spectra of the group I compounds, of a band at about 400 mμ which is absent from the spectra of the group 11 compounds. Infrared spectra are reported for all the compounds studied and a partial assignment has been made. / Science, Faculty of / Chemistry, Department of / Graduate

An apparatus for the study of positron annihilation containing some novel new features has been constructed and has been used to study disordered copper alloys in order to investigate the value of this technique in determining the electron momentum distribution. The concentrated alloys Cu₉₀Al₁₀ Cu₈₅Zn₁₅, Cu₇₀Zn₁₅Ni₁₅ and Cu₆₀Ni₄₀ have been studied and effects attributed to the details of the Fermi surface of these alloys observed. In particular, the [lll} necks in the Fermi surfaces of these alloys have been observed and the widths of these necks measured. The cutoffs corresponding to the Fermi radius kf of these alloys have been measured. An anisotropy in the annihilation of positrons with electrons in the filled Brillouin zones has been measured and an unusual effect attributed to the d-band electrons of these alloys has been observed. / Science, Faculty of / Physics and Astronomy, Department of / Graduate

An analytical technique for the differentiation of biologically active copper (Cu) in seawater was developed. The procedure involves passing a seawater sample through an ion exchange resin of the sulponate type until complete breakthrough of metal ion is achieved. The sorbed Cu is then eluted and its total concentration is determined by anodic stripping voltammetry. Comparison with Cu adsorption from standard seawater samples of similar composition, pH, and ionic strength yields a Cu equivalent measurement that is related to the free cupric ion activity of the sample. Since the cupric ion is believed to be the toxic form of the metal, the Cu equivalent measurement can be related to the biologically active fraction of Cu. The measurement of biologically active Cu by the resin technique was verified by comparing the analytical results with results from phytoplankton bioassays. Tests were first conducted in artificial seawater that had its chemistry well defined and where model organic ligand (EDTA, NTA, histidine and glutamic acid) were used to control the speciation of the metal. In the experiments using the organic ligands EDTA, NTA, or glutamic acid added to Cu spiked artificial seawater, a strong relationship between the Cu equivalent values and growth rates of the bioassay organism was found (r=0.92). However, in experiments with histidine, this relationship was much weaker and was attributed to the adsorption of positively charged Cu-histidine complexes onto the resin. The adsorption of these complexes results in overestimating the amount of biologically active Cu present in the sample. The few studies on the electrochemical nature of organic complexing agents in seawater suggests, however, that most are negatively charged. Thus the technique would be suitable in many seawater systems. The analytical and bioassay techniques were then applied to natural seawater samples collected from five depths in a local fjord. A discrepancy was found between some of the bioassay and resin test results. However, the discrepancy was attributed to a physiological Cu-Mn interaction in the bioassay organism and not to a problem with the resin technique. / Science, Faculty of / Earth, Ocean and Atmospheric Sciences, Department of / Graduate

Physical and mathematical modelling studies have been performed to investigate liquid flow driven by a horizontally injected gas. The experimental work consisted of water velocity measurements made at 100 locations within a plexiglass tank. Air was introduced into the tank through a series of side-mounted tuyeres, and the effect of air flowrate on water recirculation velocity was observed. The results of the experiments indicate that the maximum water velocity occurs at the water surface. The effect of bubbles coalescing from adjacent tuyeres was observed with increasing air flowrate, and was found to diminish the water recirculation rate. The mathematical model employed a variant of the Marker and Cell (MAC) technique to compute fluid flow with a free surface. The model predictions indicate that the flow in the experimental tank is largely driven by water flowing across the free surface. Based on this knowledge, qualitative predictions of the flow regimes in a Peirce-Smith copper converter and a zinc slag fuming furnace were made. / Applied Science, Faculty of / Mining Engineering, Keevil Institute of / Graduate

This study investigates the geological setting of the Harper Creek copper deposit. The relation of the deposit to structure and stratigraphy as well as the age and nature of the mineralization are discussed. Copper mineralization is confined to tabular-shaped zones within metasedimentary and metavolcanic rocks of the Eagle Bay Formation. Although mineralization does not appear to be stratigraphically controlled, stratigraphy was important for the locallization of higher-grade material. Large-scale structures appear to have had an important role in the channeling of 'ore-forming' fluids. The deposit is thought to be genetically related to the formation of a large east-west oriented antiform. Mineralizing fluids of probable hydrothermal metamorphic origin migrated into this structure and replaced favorable host rocks. Although tenuous, evidence presented suggests the age of mineralization is between Upper Triassic (Karnian or Lower Norian) and Lower Jurassic-Upper Triassic. / Science, Faculty of / Earth, Ocean and Atmospheric Sciences, Department of / Graduate

The sensitivitiy of several species of marine phytoplankton to copper was investigated. No specific trends were found with respect to any general differences between diatoms and dinoflagellates or between different sized cells. Further investigation using a single bioassay species, Nitzschia lonqissima, indicate it to be very sensitive to cupric ion activity. Several physiological systems appear to be affected to different degrees, with cell division being more affected than photosynthetic pigment production or ¹⁴C uptake. The activity of the enzyme nitrate reductase is greatly increased by the addition of low concentrations of copper. / Science, Faculty of / Zoology, Department of / Graduate

The reaction of a number of (trialkylstannyl)copper reagents with 2-alkynoates, N,N-dimethyl-2-alkynaraides and 1-alkynes is described. It has been found that the (trimethylstannyl)copper reagents 14 and 43-46 efficiently transfer the trimethylstannyl group to oc-alkynoates. Reagent 14 (THF, -48°C) provided predominantly the (Z)-3-trimethyl-stannyl-2-alkenoate (22), reagents 44 and 45 (THF, -48°C) afforded essentially exclusively the corresponding (E) isomer 21, while reagents 43 and 46 gave a mixture of isomers. Using the above methodology, ethyl 2-pentynoate was converted into either (Z)- or (E)-3-( tri-n-butylstannyl)-2-pentenoate. The (E) isomer was converted into the vinylstannane 188 which was transformed (MeLi, THF, -20°C) into the corresponding stereochemically homogeneous vinyllithium reagent and elaborated into the acyl portion of (±)-triophamine (172), a diacylguanidine recently isolated from Triopha catalinae. Reaction of 2-alkynoates with excess 44 or 45 (THF, 0°C) afforded, as essentially the only products, (E)-2,3-bis(trimethyl-stannyl)-2-alkenoates (115). One member of this new class of compounds, ester 114 (=115, R = Me, R' = Et) was selectively transmetalated (MeLi, THF, -98°C) and the resultant nucleophilic species was allowed to react with a number of reactive electrophiles to produce esters of general structure 141. / Science, Faculty of / Chemistry, Department of / Graduate

This thesis focuses on three aspects of long-run planning for mineral-dependent economies: (i) modelling mineral depletion for optimal capital accumulation; (ii) specification and estimation of a mining cost function and a non-mining production function; and (iii) measurement of capital and natural resource stocks. Zambia, a country totally dependent on copper, is used as a case study. The planning model integrates the Ramsey capital model with the Hotelling-Scott exhaustible resource model, utilizing recent advances in dynamic optimization and duality theory. The optimal rate of resource extraction requires that marginal variable cost plus user cost be equal to the world price of the mineral. The user cost of the resource grows at the rate of interest plus the rate of population growth minus the effect of depletion on extraction cost. The optimal allocation of resource revenues equates the marginal benefits from alternative uses: (i) current consumption to raise the standard of living of a growing population; (ii) mining investment to maintain production in the face of deteriorating resource quality; and (iii) non-mining investment to create an industrial base as an alternative to the depleting resource. A variable cost function (VCF) for the mining industry is derived from the assumption that the mining firm minimizes the variable cost of producing a given output. The parameters of a translog VCF for Zambian copper mining are estimated and found to be consistent with the underlying theory. It is also found that domestic labour is only imperfectly substitutable for imported machinery and that labour demand is not very responsive to changing wages. A substantial portion of the empirical contribution is the construction of comprehensive data series for Zambia using the perpetual inventory approach to capital stocks, Divisia, Indexes, and the neoclassical theory of rental prices. Production figures for individual mines are used to construct aggregate cumulative series to which a curve of diminishing increments is fitted to obtain andestimate of the Zambian copper resource. / Arts, Faculty of / Vancouver School of Economics / Graduate

This thesis is based on research in Cu-catalyzed electrophilic trifluoromethylation and exploiting Cu/Cu2O nanowires with novel catalytic reactivity for developing of catalytic and greener synthetic methods. A large number of biological active pharmaceuticals and agrochemicals contain fluorine substituents (-F) or trifluoromethyl groups (-CF3) because these moieties often result in profound changes of their physical, chemical, and biological properties, such as metabolic stability and lipophilicity. For this reason, the introduction of fluorine or trifluoromethyl groups into organic molecules has attracted intensive attention. Among them, transition metal-catalyzed trifluoromethylation reactions has proved to be an efficient and reliable strategy to construct carbon-fluorine (C-F) and carbontrifluoromethyl (C-CF3) bond. We have developed a catalytic process for the first time for trifluoromethylation of terminal alkynes with Togni’s reagent, affording trifluoromethylated acetylenes in good to excellent yields. The reaction is conducted at room temperature and exhibits tolerance to a range of functional groups. Derived from this discovery, the extension of work of copper catalyzed electrophilic trifluoromethylation were investigated which include the electrophilic trifluoromethylation of arylsulfinate salts and electrophilic trifluoromethylation of organotrifluoroborates. Because of growing environmental concern, the development of greener synthetic methods has drawn much attention. Nano-sized catalysts are environment-friendly and an attractive green alternative to the conventional homogeneous catalysts. The nano-sized catalysts can be easily separated from the reaction mixture due to their insolubility and thus they can be used recycled. Notably, because of the high reactivities of nano-sized metal catalysts, the use of ligands can be avoided and the catalysts loadings can be reduced greatly. Moreover, the nano-sized catalysts can increase the exposed surface area of the active component, thereby enhancing the contact between reactants and catalyst dramatically. Based on the above-mentioned concepts and with the aim of achieving one “green and sustainable” approach, C-S bond formation and click reactions catalyzed by Cu/Cu2O nanowires were investigated. It was found that the recyclable core-shell structured Cu/Cu2O nanowires could be applied as a highly reactive catalysts for the cross-coupling reaction between aryl iodides and the cycloaddition of terminal alkynes and azides under ligand-free conditions. Furthermore, these results were the first report for the crosscoupling reaction and click reaction catalyzed by one-dimensional (1D) copper nanowires.

Depuis des décennies, la chimie du fluor est un domaine suscitant un fort intérêt. Bien que de nombreuses méthodologies originales et élégantes aient été développées pour introduire des groupements fluorés variés, le résidu CF2PO(OEt)2 reste encore peu étudié. Cela contraste avec ses propriétés uniques et à hautes valeurs ajoutées. En effet, le motif CF2PO(OEt)2 s'est avéré être un bioisostère métaboliquement stable du groupement phosphate, ce dernier étant particulièrement instable in vivo en comparaison. En conséquence, des approches pour incorporer ce motif au sein de molécules ont été développées bien qu'encore limitées à un nombre restreint de transformations. Dans le cadre de cette thèse, nous souhaitons proposer une méthode générale et directe pour accéder à des molécules contenant le groupement CF2PO(OEt)2. La première partie de cette thèse a été dédiée à l'introduction du motif CF2PO(OEt)2 sur des sels d'iodonium comportant un substituant aryle, heteroaryle, ou dérivés d'alcènes et d'alcynes, mettant en jeu la génération d'une espèce de type CuCF2PO(OEt)2 (Chapitre II). Puis, l'utilité et la généralité de cette transformation a été démontrée lors de la fonctionnalisation de dérivés de type R-X (R = vinyle, allyle et benzyle) ainsi que des disulfures en tant qu'électrophiles. Par ailleurs, une réaction de couplage de type Ullmann réalisée à température ambiante a été étudiée. Finalement, la réactivité divergente de l'espèce CuCF2PO(OEt)2 envers les α-diazoesters, par un simple changement du sel de cuivre, a été examinée (Chapitre III). Cette approche a été étendue par la suite aux dérivés d'α-bromocétones afin d'offrir une voie d'accès aux cétones contenant un motif SCF2PO(OEt)2 en position α (Chapitre IV). / Since several decades, the organofluorine chemistry is a research area of strong interest. While plenty of original and elegant methodologies were developed to introduce various fluorinated groups, the CF2PO(OEt)2 residue was scarcely spotlighted. This contrasts with its unique and highly valuable properties. Indeed, the CF2PO(OEt)2 moiety proved to be a metabolically stable bioisoster of the in vivo unstable phosphate group. As a result, approaches to incorporate this motif onto molecules were developed albeit still restricted to few transformations. In this PhD thesis, we would like to propose a general and straightforward method to access CF2PO(OEt)2-containing molecules. A first part was dedicated to the introduction of the CF2PO(OEt)2 motif on aryl, heteroaryl, vinyl and alkynyl iodonium salts, by generating the CuCF2PO(OEt)2 species (Chapter II). Then, the utility and the generality of this transformation were further demonstrated using R-X (R = vinyl, allyl and benzyl) as well as disulfides as the electrophiles. Besides, a Ullmann-type cross-coupling reaction proceeding at room temperature was also studied. Finally, the divergent reactivity of the CuCF2PO(OEt)2 species toward α-diazoesters, by a simple change of copper salt, was investigated (Chapter III). This approach was then extended to α-bromoketone derivatives to access the a-SCF2PO(OEt)2 ketones (Chapter IV).