No description available.

Calcium carbonate minerals (CaCO3) are important for our understanding of past marine conditions as well as tools for constructing paleoclimate. However, very little experimental work has been done to determine the influence of oxygen depletion on the geochemistry of CaCO3. To determine how oxygen depletion affects elemental incorporation and partitioning, aragonite was grown inorganically in artificial seawater at pressures of 1 atm and 5 bars (0.1%CH4-N2 mixture). Solution of Na2CO3 was used to induce aragonite precipitation. N2 was bubbled through solution in order to minimize oxygen content and iron powder was used to trap remaining O2. Experimental products (aragonite and fluid) were analyzed with ICP-MS, and isotope ratio mass spectrometer. Results suggest that Eh affects incorporation of Mn, S, Cu, and V into aragonite. No methane oxidation was observed.

This PhD thesis is focused on the development of novel low-oxidation state main group catalysis for organic synthesis. More specifically, the major objective has been to explore and design non-toxic and effective catalysts based on the following isoelectronic species: nitreones [nitrogen(I)], carbones [carbon(0)], and silylones [silicon(0)]; the corresponding central nonmetal atom in these molecules is in the formal low-oxidation state ‘+I’ and ‘0’, respectively. These species have been calculated to be strong Lewis and Brønsted bases. In addition, compared with established base catalysts such as N-heterocyclic carbenes (NHCs), nitreones, carbones, and silylones formally possess an additional lone pair of electrons at the central atom. In turn, these species may be used in base catalysis or as ligands in metal catalysis, and in the context of frustrated Lewis pair (FLP) or dual catalysis. The Lewis basicity of these N(I), C(0), and Si(0) compounds has been assessed with 11B NMR analysis using a variety of boron Lewis acids. These boron binding data have been compared with results obtained using NHCs as a Lewis base. Nitreones –more specifically cyclopropen-imines– have been explored in base catalysis. These N(I) Lewis bases have been uncovered to catalytically activate a variety of silicon-based pro-nucleophiles for subsequent bond formation with carbonyl and imine derivatives as well as aziridines. Successfully used pro-nucleophiles include TMS–CN, TMS– CF3, TMS–N3, and TMS–Cl. The characteristic features of this unprecedented cyclopropenimine Lewis base catalysis include low catalyst loading, mild reaction conditions, and broad substrate scopes. Various “normal” imines have proved to be catalytically inactive under the same conditions. In a similar context, carbones and silylones have been used to develop novel catalytic umpolung reactions, which turned out to be too challenging at this stage. Importantly though, silylones have been shown to activate the B–H bond of suitable pro-nucleophiles. Finally, several carbone–metal complexes have been synthesized and characterized. These novel species may be used in Lewis acid or dual catalysis after appropriate activation of the corresponding metal site.

No description available.

The oxidation state, reflected in the oxygen fugacity (fO2), of the lithospheric mantle is both laterally and vertically heterogeneous. Depth-fO2 profiles from kimberlite-borne peridotitic mantle xenoliths from the Bultfontein kimberlite, Kimberley, South Africa and the A154-N and A154-S kimberlites of the Diavik Mine, NWT, Canada were constructed by measuring ferric iron concentrations in garnets using the flank method. These data demonstrate that mantle metasomatic re-enrichment processes had a significant effect on fO2. In the garnet stability field, the Kaapvaal lithospheric mantle becomes progressively more reducing with increasing depth from Δlog fO2 (FMQ) of -2 at 110 km to -4 at 210 km. The lithospheric mantle beneath Diavik is vertically layered with respect to its bulk and trace-element composition. The shallow ‘ultradepleted’ layer is oxidized, to the point that carbonate rather than graphite is the anticipated carbon host. The deeper layer is more fertile and has fO2 conditions extending down to Δlog fO2 (FMQ) -3.8. Deviations from predicted depth-fO2 trends in both xenolith localities result from metasomatic re-enrichment caused by transient fluids and melts. Diamond formation in the Kaapvaal lithospheric mantle may have occurred through the infiltration of reduced fluids into relatively more oxidized mantle. Trace-element concentrations in garnets preserve evidence of two distinct melt metasomatic enrichment events. One was a craton-wide event that is commonly observed in garnet peridotite xenoliths and xenocrysts worldwide; the other was melt infiltration event, preserved as MARID xenoliths, related to the eruption of the Group 2 kimberlites in the western portion of the Kaapvaal craton. The effect of the former melt metasomatism on fO2 is unclear ambiguous whereas the MARID event was clearly oxidizing. Diavik xenoliths preserve evidence for events similar to the fluid and ‘common’ melt metasomatism seen in the Bultfontein samples. Fluid metasomatism affected the entire depth range of xenoliths sampled from Diavik and was oxidizing. A stage of melt metasomatism affected only the deeper (>140 km) portion of the lithospheric mantle and had an overall reducing effect. The observation of sharp-edged octahedral diamonds in microxenoliths affected by the fluid metasomatic event may indicate that this was a major diamond-forming event in the mantle beneath Diavik.

This PhD thesis is focused on the development of novel catalysis with low-oxidation main group species, mainly based on the group 13 element gallium, a relatively abundant, inexpensive, and low-toxic metal. Gallium in its stable high-oxidation state ‘+III’ is a commonly used Lewis acid catalyst in organic synthesis. In contrast, gallium in its less stable low-oxidation state ‘+I’ is under-explored, but may display both acceptor and donor properties at a single site (ambiphilicity). Based on the hypothesis that potentially ambiphilic gallium(I) –oxidatively generated in situ from gallium(0) using a silver salt– may activate both basic and acidic reagents, various gallium(I)-catalyzed carbon–carbon bond formations have been developed. These include catalytic C–O and C–B bond activations of electrophiles (acetals and aminals) and pro-nucleophiles (allyl and allenyl boronates), respectively. Gallium(III) and other metal Lewis acids have proved to be ineffective. These results represent the first catalytic use of gallium(0) in organic synthesis and a rare example of gallium(I) catalysis. The identity of the gallium(I) catalyst and its regeneration have been confirmed by 71Ga NMR analysis, and a reactive allyl–Ga(I) intermediate has been detected for the first time. In combination with 11B NMR and HRMS analyses, an SN1 reaction mechanism has been proposed. Importantly, the potential for asymmetric gallium(I) catalysis has been demonstrated using a chiral silver co-catalyst (40% ee). This gallium(I) chemistry has proved to be applicable to the catalytic activation of other electrophiles, including ethers or aldehydes, and pro-nucleophiles such as boranes, silanes, or tin-based reagents. Finally, the potential of a related low-oxidation aluminium catalyst has been explored for C–C bond formation.

The sandstone-hosted McArthur River Zone 4 U ore body and alteration system, located in the Athabasca Basin, are the focus of a detailed mineralogical and geochemical study aimed at reconstructing its evolution. The oxidation state of Fe in clay alteration from Zone 4 is measured using 57Fe Mössbauer spectroscopy and compared with other mineralized and barren sandstone-hosted alteration systems in the Athabasca Basin. The aim is to ascertain the role of Fe in forming U deposits and determine whether Fe oxidation state in alteration minerals can indicate proximity to mineralization. At Zone 4, early diagenetic kaolin is overprinted by zones of dravite, illite, chlorite, and late kaolinite forming around the P2 fault. Uranium mineralization occurred at ca. 1600 Ma and was triggered by mixing between oxidizing U-bearing basinal fluids and reducing basement-modified basinal fluids, the latter forming when basinal fluids interacted with basement lithologies. Early pre-ore silicification in the lower 200 metres of the Manitou Falls Formation above the ore body created favourable conditions for mineralization by focusing basinal fluids into the reduction site and enhancing ore preservation. However, it obstructed the post-ore migration of radiogenic Pb and U pathfinder elements from the deposit and limited the extent of hydrothermal sudoite alteration in the overlying strata. Sandstone-hosted alteration systems in the Athabasca Basin are commonly surrounded by an outer illite and an inner chlorite zone. Illites have high Fe3+/ƩFe ratios characteristic of formation from oxidizing basinal fluids, whereas, chlorites have lower and more varied Fe3+/ƩFe ratios, reflecting their origin from reducing, Fe2+-bearing basement-derived fluids having undergone variable mixing with oxidizing basinal fluids. Chlorites in mineralized systems where fluid-mixing occurred, such as at McArthur River Zone 4 and Maurice Bay, record higher Fe3+/ƩFe ratios than barren systems where fluid-mixing did not, such as at Wheeler River Zone K and Spring Point. The scarcity of U-bearing basinal fluids available for mixing with Fe2+-bearing basement fluids is a critical geochemical factor precluding mineralization in barren sandstone-hosted systems. The Fe3+/ƩFe ratio of chlorites has potential applications for discriminating barren and mineralized systems and as spatial vectors to ore when coupled with Pb isotope ratios. / Thesis (Master, Geological Sciences & Geological Engineering) -- Queen's University, 2012-11-01 14:08:33.51

Electron affinity is one of the most important parameters that guide chemical reactivity. Halogens have the highest electron affinities among all elements. A class of molecules called superhalogens has electron affinities even greater than that of Cl, the element with the largest electron affinity (3.62 eV). Traditionally, these are metal-halogen complexes which need one electron to close their electronic shell. Superhalogens have been known to chemistry for the past 30 years and all superhalogens investigated in this period are either based on the 8-electron rule or the 18-electron rule. In this work, we have studied two classes of unconventional superhalogens: borane-based superhalogens designed using the Wade-Mingo’s rule that describes the stability of closo-boranes, and pseudohalogen based superhalogens. In addition, we have shown that superhalogens can be utilized to build hyperhalogens, which have electron affinities exceeding that of the constituent superhalogens, and also to stabilize unusually high oxidation states of metals.

This thesis extends our fundamental knowledge in the area of high oxidation state chemistry of xenon trioxide, XeO3. Oxygen coordination to the Xe(VI) atom of XeO3 was observed in its adducts with triphenylphosphine oxide, [(C6H5)3PO]2XeO3, dimethylsulfoxide, [(CH3)2SO]3(XeO3)2, pyridine-N-oxide, (C5H5NO)3(XeO3)2, and acetone, [(CH3)2CO]3XeO3. The crystalline adducts were characterized by low-temperature single-crystal X-ray diffraction and Raman spectroscopy. Unlike solid XeO3, which detonates when mechanically or thermally shocked, the solid [(C6H5)3PO]2XeO3, [(CH3)2SO]3(XeO3)2, and (C5H5NO)3(XeO3)2 adducts are insensitive to mechanical shock, but undergo deflagration when exposed to a flame. Both [(C6H5)3PO]2XeO3 and (C5H5NO)3(XeO3)2 are air-stable at room temperature. The xenon coordination sphere in [(C6H5)3PO]2XeO3 is a distorted square pyramid and provides the first example of a five-coordinate Xe center in a XeO3 adduct. The xenon coordination sphere of the remaining adducts are distorted octahedral comprised of three equivalent Xe---O secondary contacts that are approximately trans to the primary Xe–O bonds of XeO3. Hirshfeld surfaces of XeO3 and (C6H5)3PO in [(C6H5)3PO]2XeO3 show the adduct is well-isolated in its crystal structure and provide a visual representation of the secondary Xe---O bonding in this adduct. Crown ethers have been known for over 50 years, but no example of a complex between a noble-gas compound and a crown ether or another polydentate ligand had been reported. Xenon trioxide is shown to react with 15-crown-5 to form the kinetically stable (CH2CH2O)5XeO3 adduct which, in marked contrast with solid XeO3, does not detonate when mechanically shocked. The crystal structure shows that the five oxygen atoms of the crown ether are coordinated to the xenon atom of XeO3. The gas-phase Wiberg bond valences and indices and empirical bond valences indicate the Xe---Ocrown bonds are predominantly electrostatic, σ-hole, bonds. Mappings of the electrostatic potential (EP) onto the Hirshfeld surfaces of XeO3 and 15-crown-5 in (CH2CH2O)5XeO3 and a detailed examination of the molecular electrostatic potential surface (MEPS) of XeO3 and (CH2CH2O)5 reveal regions of negative EP on the oxygen atoms of (CH2CH2O)5 and regions of high positive EP on the xenon atom that are also consistent with σ-hole bonding. Reactions of crown ethers with HF acidified aqueous solutions of XeO3 at room-temperature yielded adducts of 12-crown-4, (CH2CH2O)4XeO3, and 18-crown-6, [(CH2CH2O)6XeO3∙2H2O]2∙HF, whereas slow cooling of a solution of XeO3 with 18-crown-6 in acetone yielded (CH2CH2O)6XeO3∙2H2O. The adducts (CH2CH2O)4XeO3 and (CH2CH2O)6XeO3∙2H2O are shock-insensitive whereas the former adduct is air-stable at room temperature. The low-temperature, single-crystal X-ray structures show the Xe atom of XeO3 coordinated to the oxygen atoms of the crown ether ring. Uncharacteristic xenon coordination numbers exceeding six (including the three primary bonds of XeO3) were observed for all crown ether adducts. Raman spectroscopy frequency shifts are consistent with complex formation and provided evidence for the 2,2,1-cryptand adduct of XeO3. Gas-phase Wiberg bond valences and indices and empirical solid-state bond valences confirmed the electrostatic nature of the Xe---O bonding interactions. Comparisons between the XeO3 and SbF3 18-crown-6, 15-crown-5, and 12-crown-4 complexes are made. Incorporation of xenon trioxide, XeO3, into inorganic polyatomic salts under ambient conditions has been observed in several mixed xenate salts; K[XeO3XO3] (X = Cl, Br), K2[XeO3SeO4]∙HF, K[(XeO3)nZO3] (Z = I, N), and M2[(XeO3)nCO3]∙xH2O (M = Na, K, Rb, Ba). Raman spectroscopy was used to identify the aforementioned compounds and K[XeO3ClO3], K[XeO3BrO3], K2[XeO3SeO4]∙HF, and Rb2[(XeO3)2CO3]∙2H2O were also characterized by low-temperature, single-crystal X-ray diffraction. The xenon atom of XeO3 is seven coordinate in K[XeO3ClO3] and six coordinate in all other compounds with Xe---O distances that are significantly less than the sum of the Xe and O van der Waals radii. These salts provide examples of XeO3 coordinated to inorganic compounds and may provide insights into the inclusion of xenon oxides in minerals. / Thesis / Master of Science (MSc)

Abstract Density functional theory (DFT) is a well-established tool for calculating the properties of materials. The volume of DFT-related publications doubles every 5–6 years, which has resulted in the appearance of continuously growing open material databases, containing information on millions of compounds. Furthermore, the results of DFT computations are frequently coupled with experimental ones to strengthen the computational findings. In this thesis, several applications of DFT related to physics and chemistry are discussed. The conductivity between MoS₂ and transition metal nanoparticles is evaluated by calculating the electronic structure of two different models for the nanoparticles. Chemical bonding of Ni to the MoS₂ host is proven by the system’s band alignment. To meet the demand for cleaner fuel, the applicability of the (103) edge surface of molybdenum disulfide in relation to the early stages of the hydrodesulfurization (HDS) reaction is considered. The occurrence of the (103) edge surface of molybdenum disulfide in the XRD patterns is explained. A method for calculating oxidation states based on partial charges using open materials databases is suggested. We estimate the applicability of the method in the case of mixed valence compounds and surfaces, showing that DFT calculations can be used for the estimation of oxidation states. / Tiivistelmä Tiheysfunktionaaliteoria (density functional theory, DFT) on yleisesti käytetty työkalu laskennallisessa materiaalitutkimuksessa. DFT:llä tuotettujen julkaisujen määrä kaksinkertaistuu 5–6 vuoden välein, minkä johdosta käytettävissä on jatkuvasti kasvava määrä avoimia materiaalitietokantoja, joihin on talletettu miljoonien yhdisteiden ominaisuuksia. DFT-laskujen tuloksia täydennetään myös usein kokeellisilla tuloksilla. Tässä työssä tarkastellaan tiheysfunktionaaliteorian sovelluksia fysiikassa ja kemiassa. MoS₂:n ja metallisten nanopartikkelien välistä johtavuutta on tutkittu mallintamalla erilaisia nanopartikkeleita. Nikkelin ja MoS₂:n välinen kemiallinen sidos selittyy systeemin energiavöiden kohdistumisella. MoS₂:n (103)-pinnan soveltuvuutta rikinpoistoreaktion varhaisissa vaiheissa on tutkittu tarkoituksena löytää uusia menetelmiä puhtaan polttoaineen tuottamiseksi. Myös (103)-pinnan esiintyminen röntgendiffraktiokuvissa selitetään. Työssä on myös esitetty menetelmä hapetustilojen laskemiseksi tietokannoista löytyvien laskettujen varausjakaumien avulla. Menetelmän soveltuvuutta on tarkasteltu erilaisille yhdisteille ja pinnoille. Tämä tarkastelu osoittaa, että DFT-tuloksia voidaan käyttää hapetustilojen laskemiseen.