Copper is an inexpensive, earth-abundant, non-toxic metal that is found to have widespread applications in catalysis. Ullmann and Ullmann-type reactions and Glaser-Hay oxidative coupling of terminal alkynes are some of the well-established copper catalyzed coupling reactions used for the construction of important organic molecules, including pharmaceuticals, commodity chemicals and polymers. Those reactions have been mainly performed homogeneously, where the removal of residual copper from the reaction mixture is a challenge. Therefore, many researchers tried supporting copper precatalysts in order to help recover, and thus reduce final product contamination. Some studies showed that copper leached significantly from the support, with others showing that leached copper has a role in the catalysis. Nevertheless, many studies reported that the used supported catalysts were recyclable and claimed catalyst's heterogeneity. In most cases, the nature of the truly active copper species is still not clear. The objectives of this thesis were (1) to assess the heterogeneity/homogeneity of active copper species in popular catalytic C-N coupling reactions with already studied catalysts, mainly a copper exchanged zeolite and copper oxide nanoparticles, and (2) to use the collected information in designing a truly heterogeneous (stable and recyclable) catalyst. Initially, and because of its shape selectivity characteristics, copper-exchanged NaY zeolite, Cu(II)Y, was chosen to study the heterogeneity of copper catalyzed amination of aryl iodide with imidazole. The collected results from conducted shape selectivity tests indicated that Cu(II)Y might be heterogeneous catalyst, but because of the used base, that is crucial for this C-N coupling reaction, the crystallinity of the zeolite structure was diminished. Therefore, it was important to support copper on a framework that is stable under the basic conditions required for this type of reaction if a heterogeneous, recyclable catalyst were to be achieved. For this purpose, cerium oxide was chosen, and copper oxide supported on cerium oxide, CuO-CeO₂, was investigated as a potential heterogeneous catalyst for C-N coupling reaction. This investigation included the role of each reaction reagent in facilitating copper leaching into solution. It was found that copper leached from the support and it was demonstrated through hot filtration tests that the leached copper species was the main active catalyst. Leaching was caused by the solvent (DMSO) as well as the used reactants and the base. Similar conclusions were drawn when this CuO-CeO₂ catalyst was used for the direct synthesis of imines from amines under aerobic conditions. Although this CuO-CeO₂ catalyst has the advantages of being more recoverable and active than unsupported CuO nanoparticles at similar copper loadings, it is not fully recyclable, as the copper catalysis occurs in solution. These findings meant that designing a truly heterogeneous catalyst for this reaction is a challenging task. Understanding the effect of each individual factor of this complicated system might help in achieving the second goal - designing a truly heterogeneous catalyst. Therefore, further studies were carried out to understand the effect of reaction conditions, including temperature, base, support, and solvent, on copper leaching. Homocoupling of terminal alkynes was chosen as a model reaction for this study, and CuO was supported on TiO₂ (10CuO-TiO₂) and on γ-Al₂O₃ (10CuO-Al₂O₃). It was found that copper interaction with the support affects the extent of leaching as well as the nature and activity of leached species. High temperature also facilitates copper leaching especially when a ligating amine, like piperidine, is present in the system.

Atmospheric particles play a crucial role in climate, visibility, air pollution, and human health. Reactions between gas-phase molecules and particles (heterogeneous reactions) affect not only the particle composition and morphology, but also the composition of the atmosphere. This thesis investigates the heterogeneous chemistry of organic mixtures and inorganic solutions coated with organic monolayers as proxies for atmospheric particles. The first topic of interest was the reaction between N₂0₅ and aqueous inorganic solutions coated with organic monolayers. The goal of this work was to better understand how organic monolayers on aqueous particles affect the mass transport and kinetics of N₂0₅ uptake by aqueous aerosols, and consequently what effectthe monolayer can have on predicted concentrations of N₂0₅ in the atmosphere. To investigate heterogeneous reactions of inorganic solutions coated with an organic monolayer a new rectangular channel flow reactor was developed. This newly developed flow reactor was described in detail and validated. Subsequently, the new flow reactor was used to study the reactive uptake of N₂0₅ on sulfuric acid solutions in the presence of a variety of 1- and 2-component monolayers with varying functional groups, solubilities, chain lengths, surface pressures, and molecular surface areas. Reactive uptake of N₂0₅ on aqueous sulfuric acid solutions was found to correlate most strongly with the molecular surface area or packing density of the monolayer. These results provide a good foundation for determining the influence of monolayers on heterogeneous reactions in the atmosphere, and highlight the need for characterization of monolayer surface properties of organic monolayers present on atmospheric particles. The second topic of interest was reactions between 0₃ and proxies for meat cooking aerosols with the goal to better understand the effect of the phase and microstructure of the mixtures on the lifetime of oleic acid (OA) in atmospheric particles. The reactive uptake of 0₃ was approximately 1 order of magnitude slower on binarysolid-liquid mixtures and multicomponent mixtures that closely represent compositions of meat-cooking aerosols compared to the liquid solutions. Lifetimes up to 75 min were obtained for these mixtures.

Abstract Cobalt-based complexes are widely used in industry and organic synthesis as catalysts for the oxidation of hydrocarbons. The Co/Mn/Br (known as "CAB system") catalyst system is effective for the oxidation of toluene. The Co/Mn/Br/Zr catalyst system is powerful for the oxidation of p-xylene, but not for the oxidation of toluene. [Co3O(OAc)5(OH)(py)3][PF6] (Co 3+ trimer 5) is more effective than [Co3O(OAc)6(py)3][PF6] (Co 3+ trimer 6) as a catalyst in the CAB catalyst system. Higher temperatures favour the oxidation of toluene. Zr 4+ does not enhance the oxidation of toluene. Zr 4+ could inhibit the oxidation of toluene in the combination of Co/Br/Zr, Co/Mn/Zr or Co/Zr. NHPI enhances the formation of benzyl alcohol, but the formation of other by-products is a problem for industrial processes. Complex(es) between cobalt, manganese and zirconium might be formed during the catalytic reaction. However, attempts at the preparation of complexes consisting of Co/Zr or Mn/Zr or Co3ZrP or Co8Zr4 clusters failed. The oxidation of cyclohexane to cyclohexanone and cyclohexanol is of great industrial significance. For the homogeneous catalysis at 50 o C and 3 bar N2 pressure, the activity order is: Mn(OAc)3 �2H2O > Mn12O12 cluster > Co 3+ trimer 6 > [Co3O(OAc)3(OH)2(py)5][PF6]2 (Co 3+ trimer 3) > Co 3+ trimer 5 > Co(OAc)2 �4H2O > [Co2(OAc)3(OH)2(py)4][PF6]-asym (Co dimerasym) > [Co2(OAc)3(OH)2(py)4][PF6]-sym (Co dimersym); whereas [Mn2CoO(OAc)6(py)3]�HOAc (Mn2Co complex) and zirconium(IV) acetate hydroxide showed almost no activity under these conditions. But at 120 o C and 3 bar N2 pressure, the activity order is changed to: Co dimerasym > Co(OAc)2 �4H2O > Co trimer 3 and Mn(OAc)3 �2H2O > Co 3+ trimer 6 > Mn2Co complex > Co 3+ trimer 5 > Co dimersym > Mn12O12 cluster. The molar ratio of the products was close to cyclohexanol/cyclohexanone=2/1. Mn(II) acetate and zirconium(IV) acetate hydroxide showed almost no activity under these conditions. Among those cobalt dimers and trimers, only the cobalt dimerasym survived after the stability tests, this means that [Co2(OAc)3(OH)2(py)4][PF6]-asym might be the active form for cobalt(II) acetate in the CAB system. Metal-substituted (silico)aluminophosphate-5 molecular sieves (MeAPO-5 and MeSAPO-5) are important heterogeneous catalysts for the oxidation of cyclohexane. The preparation of MeAPO-5 and MeSAPO-5 and their catalytic activities were studied. Pure MeAPO-5 and MeSAPO-5 are obtained and characterised. Four new pairs of bimetal-substituted MeAPO-5 and MeSAPO-5(CoZr, MnZr, CrZr and MnCo) were prepared successfully. Two novel trimetal-subtituted MeAPO-5 and MeSAPO-5 (MnCoZr) are reported here. Improved methods for the preparation of four monometal-substituted MeAPO-5 (Cr, Co, Mn and Zr) and for CoCe(S)APO-5 and CrCe(S)APO-5 are reported. Novel combinational mixing conditions for the formation of gel mixtures for Me(S)APO-5 syntheses have been developed. For the oxidation of cyclohexane by TBHP catalysed by MeAPO-5 and MeSAPO-5 materials, CrZrSAPO-5 is the only active MeSAPO-5 catalyst among those materials tested under conditions of refluxing in cyclohexane. Of the MeAPO-5 materials tested, whereas CrCeSAPO-5 has very little activity, CrZrAPO-5 and CrCeAPO-5 are very active catalysts under conditions of refluxing in cyclohexane. MnCoAPO-5, MnZrAPO-5 and CrAPO-5 are also active. When Cr is in the catalyst system, the product distribution is always cyclohexanone/cyclohexanol equals 2-3)/1, compared with 1/2 for other catalysts. For MeAPO-5, the activity at 150 o C and 10 bar N2 pressure is: CrZrAPO-5 > CrCeAPO-5 > CoZrAPO-5. For MeAPO-5 and MeSAPO-5, at 150 o C and 13 bar N2 pressure, the selectivity towards cyclohexanone is: CrZrAPO-5 > CrZrSAPO-5 > CrCeAPO-5 > CrAPO-5 > MnCoAPO-5 > MnZrAPO-5; and the selectivity towards cyclohexanol is: MnZrAPO-5 > CrZrAPO-5 > MnCoAPO-5 > CrZrSAPO-5 > CrCeAPO-5 > CrAPO-5. Overall the selectivity towards the oxidation of cyclohexane is: CrZrAPO-5 > CrZrSAPO-5 > CrCeAPO-5 > CrAPO-5 > MnCoAPO-5 > MnZrAPO-5. The amount of water in the system can affect the performance of CrCeAPO-5, but has almost no effect on CrZrAPO-5. Metal leaching is another concern in potential industrial applications of MeAPO-5 and MeSAPO-5 catalysts. The heterogeneous catalysts prepared in the present work showed very little metal leaching. This feature, coupled with the good selectivities and effectivities, makes them potentially very useful.

Thesis (Ph. D.)--University of Virginia, 2007. / Includes bibliographical references. Also available online through Digital Dissertations.

Thesis (M.S.)--West Virginia University, 1998. / Title from document title page. "Dec. 3, 1998." Document formatted into pages; contains vii, 19 p. : ill. Includes abstract.

Thesis (Master)--İzmir Institute of Technology, İzmir, 2005. / Keywords: Palladium, Immobilization, Heck Reaction, Palladium-N-Heterocyclic Carbene, Carbon-Carbon Coupling. Includes bibliographical references (leaves. 89-104).

Thesis (Master)--İzmir Institute of Technology,İzmir, 2004 / Includes bibliographical references (leaves. 118-134).

Thesis (Ph. D.)--York University, 2002. Graduate Programme in Chemistry. / Typescript. Includes bibliographical references. Also available on the Internet. MODE OF ACCESS via web browser by entering the following URL: http://wwwlib.umi.com/cr/yorku/fullcit?pNQ71976.

Thesis (M. Phil.)--Hong Kong University of Science and Technology, 2004. / Includes bibliographical references (leaves 125-135). Also available in electronic version. Access restricted to campus users.

Thesis (M.S. in Computer Science)--Naval Postgraduate School, March 2005. / Thesis Advisor(s): Gurminder Singh, Su Wen. Includes bibliographical references (p. 81). Also available online.