This thesis details the use of aromatic ions, especially aminocyclopropenium ions, as empowering design elements in the development of new chemical reactions, organic catalysts and polymeric materials. A particular focus is placed throughout on understanding the relationship between the structure of aromatic ions and their performance in these novel applications. Additionally, the benefits that aromatic ions provide in these contexts are highlighted. The first chapter briefly summarizes the Lambert Group's prior efforts toward exploiting the unique reactivity profiles of aromatic ions in the context of new reaction design. Also provided in the first chapter is a comprehensive literature review of aminocyclopropenium ions, upon which the majority of advances described in this thesis are based. To set the stage for the first application of aminocyclopropenium ions, Chapter 2 provides an account of existing highly Brønsted basic functional groups, including guanidines, proazaphosphatranes and iminophosphoranes. The provided review on the synthesis and use in asymmetric catalysis of these bases indicates that there is a high need for conceptually new Brønsted basic functional groups. To address this need, the development of chiral 2,3-bis(dialkylamino)cyclopropenimines as a new platform for asymmetric Brønsted base catalysis is described in Chapter 3. This new class of Brønsted base is readily synthesized on scale, operates efficiently under practical conditions, and greatly outperforms closely related guanidine-based catalysts. Structure-activity relationship studies, mechanistic experiments and computational transition state modeling are all discussed in the context of asymmetric glycinate imine Michael reactions in order to arrive at a working model for cyclopropenimine chemistry. Cumulatively, this chapter provides a "user's guide" to understanding and developing further applications of 2,3-bis(dialkylamino)cyclopropenimines. The use of our optimal chiral 2,3-bis(dialkylamino)cyclopropenimine catalyst to promote asymmetric Mannich reactions of glycinate imines and N-Boc-aldimines is described in Chapter 4. The products of this transformation are optically enriched diamino acid derivatives, an important motif widely utilized in medicinal and synthetic chemistry. Importantly, unlike existing methods, our technology promotes reactions between tert-butyl glycinate and aliphatic N-Boc-aldimine substrates. A preparative-scale reaction is demonstrated and derivatization of its product to several valuable chiral compounds is shown. Chapter 5 describes the use of tris(dialkylamino)cyclopropenium (TDAC) ions as a new class of onium-like catalyst. A simple TDAC chloride salt is prepared on a 75-gram scale and its use as a phase transfer catalyst for a variety of reactions is demonstrated. This same salt is also utilized as an epoxide opening catalyst for a variety of transformations, including the fixation of carbon dioxide. Chapter 6 briefly highlights several continued applications of the chemistry advanced throughout this thesis. First, the work of other members of the Lambert Group toward the continued development of cyclopropenimine chemistry is described. Second, a broad initiative between the Lambert and Campos Groups at Columbia University focused on the synthesis and application of TDAC-based polymers is introduced. Lastly, the identification of a previously unknown equilibrium between fulvenes and imines/aldehydes in the context of a new mode of catalysis is presented.

No description available.

Silicon holds a privileged position in organic chemistry as the carbon-silicon bond can be utilised in many important transformations. As such, developing practical and efficient methods for the enantioselective and regioselective insertion of silicon into organic molecules is a worthy challenge in chemical synthesis. To this end, we have developed an affordable copper-catalysed protocol for the asymmetric silylation of lactones, lactams and amides, providing silylated products with up to > 99:1 er and in good yields. Furthermore, we have demonstrated the synthetic utility of this protocol in the target synthesis of natural or biologically active molecules. We also present the first copper-catalysed silylation of allenes using a silylborane reagent. This affords useful allyl- or vinylsilane building blocks with high regioselectivity, efficiency and a large functional group tolerance. The allylcopper intermediates can be intercepted by aldehydes in a diastereoselective three-component coupling to furnish homoallylic alcohols. We extend this concept to the copper-catalysed three-component coupling of boron, allenes and imines, providing access to homoallylic amines with a vinylborane motif.

Luk To. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2005. / Includes bibliographical references (leaves 115-123). / Abstracts in English and Chinese. / Contents --- p.i / Acknowledgement --- p.ii / Abstract --- p.iii / Abbreviation --- p.vi / Chapter 1. --- Introduction --- p.1 / Chapter 1-1 --- Background --- p.1 / Chapter 1-2 --- Sharpless Epoxidation --- p.2 / Chapter 1-3 --- Mn-Salen Complexes for Epoxidation --- p.4 / Chapter 1-4 --- Oxaziridinium Salts --- p.6 / Chapter 1-5 --- Dioxiranes --- p.9 / Chapter 1-6 --- Asymmetric Epoxidation by Dioxirane --- p.12 / Chapter 2. --- Results and Discussion --- p.31 / Chapter 2-1 --- Epoxidation of trαns-disubstituted and trisubstituted alkenes catalyzed by L-αrαbino-4-uloses --- p.31 / Chapter 2-2 --- Epoxidation of cis-alkenes catalyzed by L-arabino-4-uloses --- p.47 / Chapter 2-3 --- Epoxidation of alkenes catalyzed by new L-arabino-4-uloses --- p.55 / Chapter 3. --- Conclusion --- p.77 / Chapter 4. --- Experimental Section --- p.80 / Chapter 5. --- References --- p.115 / Chapter 6. --- Appendix --- p.124

by Yeung Kwan Wing. / Thesis submitted in: 2002. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2003. / Includes bibliographical references (leaves 68-73). / Abstracts in English and Chinese. / Contents --- p.i / Acknowledgement --- p.ii / Abstract --- p.iii / Abbreviation --- p.v / Chapter 1. --- Introduction --- p.1 / Chapter 1-1 --- Background --- p.1 / Chapter 1-2 --- Sharpless Epoxidation --- p.2 / Chapter 1-3 --- Mn-Salen Complexes for Epoxidation --- p.4 / Chapter 1-4 --- Oxaziridinium Salts --- p.6 / Chapter 1-5 --- Dioxiranes --- p.7 / Chapter 1-6 --- Asymmetric Epoxidation by Dioxirane --- p.11 / Chapter 2. --- Results and Discussion --- p.28 / Chapter 2-1 --- C-Glycoside Ulose Catalyst derived from L-arabinose --- p.28 / Chapter 2-2 --- Dioxirane epoxidation catalyzed by L-arabino-4-uloses --- p.30 / Chapter 3. --- Experimental Section --- p.51 / Chapter 4. --- References --- p.68 / Chapter 5. --- Appendix --- p.74

Transition metals represent some of the first catalysts used in industrial processes and are still used today to produce many of the most needed chemicals. Adopting from ancient metallurgical techniques, it followed that the performance of these basic transition metals can be refined by adding multiple components. Since that time, improvements to these alloy catalysts has been mostly incremental due to the difficulty of producing new catalysts experimentally and a lack of fundamental understanding of the underlying physics. More recently, computational chemistry has proven itself an increasingly effective means for identifying these underlying physics. Through the use of d-band interactions of adsorbates with the surface, basic adsorption characteristics can be predicted across transition metals with limited initial information. However, although these models function well as high-level screening tools, much work is yet to be done before optimal catalysts can be comfortably designed from properties which experimentalists can directly control. This remains particularly challenging for alloy modeling, primarily due to the large number of possible atomic configurations, even for two metal systems. This work focuses on developing the methods for modeling optimal reaction properties at the surface of a transition metal alloy. Based on thermodynamic equilibrium between the surface, bulk, and gas reservoir, a model for the prediction of segregation under vacuum and adsorbate conditions can be predicted. Furthermore, by relating strain in the bulk lattice constant to the adsorption energies of varying local active sites, the optimal surface compositions can be related to bulk composition; a feature which can easily be selected for. Although useful for identifying trends across bulk composition space, these methods are limited to a small subset of active site configurations. To capture the complexity of more sophisticated processes, such as segregation, higher-timescale methods are required. Traditional computational tools are often too expensive to implement for these methods, and as such, they are usually completed with less-accurate potentials. In this work, we demonstrate that machine learning techniques have improved accuracy compared to physical potentials. We then go on to demonstrate how this improved accuracy can lead to experimentally accurate predictions of segregation.

No description available.

A molécula de 3-metilpiperidina (3-Mepip) foi investigada como ligante ancilar em um novo complexo do tipo [RuCl2(PPh3)2(amina)] em polimerização via metátese de olefinas ciclicas por abertura de anel (ROMP) de norborneno (NBE) e norbornadieno (NBD). A síntese do novo complexo foi realizada partindo-se do complexo precursor [RuCl2(PPh3)3], e foi caracterizado por: EPR, análise elementar de CHN, infravermelho (FTIR) e RMN de 31P. Com base nos resultados obtidos é possível propor um complexo pentacoordenado com geometria pirâmide de base quadrada (PBQ), estando os íons cloretos trans-posionados no plano equatorial da esfera de coordenação do metal, com a amina ocupando a posição apical da pirâmide devido ao seu forte caráter doador σ. As reações de ROMP dos monômeros NBE e NBD utilizando o novo complexo foram realizadas em atmosfera de argônio em função da razão molar de molar [monômero]/[Ru] (1000, 3000, 5000, 7000 e 10000), tempo (5, 30 e 60 min) e temperatura (25 e 50 °C). Com um volume de 5 µ de etildiazoacetato (EDA), 25 °C e uma razão molar de 5000 de monômero a 5 min, obteve-se 65 % de poliNBE com Mn = 0,8 x 105 e IPD igual a 1,9. Os polímeros obtidos com NBD apresentaram um rendimento em torno de 20% a 25 °C por 5 min. Reações de polimerização em atmosfera aberta resultaram em valores de rendimento próximos dos observados em atmosfera de argônio, sugerindo dessa forma que o novo complexo é resistente a processos oxidativos provocados pelo O2 da atmosfera ambiente. As reações de polimerização foram realizadas na presença de outros diazocompostos benzildiazoacetato (BDA) e tertbutildiazoacetato (TBDA) como fontes de carbenos, afim de avaliar a influência eletrônica e estérica provocada pelos diferentes grupo R desses diazocompostos. Foi observado que o etildiazoacetato (EDA) apresentou os melhores valores de rendimento dos polímeros isolados, provavelmente devido ao balanço nas características estéricas e eletrônicas desse diazo frente ao centro de Ru(II). / The 3-methylpiperidine (3-Mepip) molecule was investigated as ancillary ligand in a novel [RuCl2(PPh3)2(amine)] type complex for ring-opening metathesis polymerization (ROMP) of norbornene (NBE) and norbornadiene (NBD). The synthesis of the new complex was performed from the precursor complex [RuCl2(PPh3)3], and it was characterized by: EPR, CHN elemental analysis, infrared (FTIR) and 31P NMR (1H). From the obtained results it was possible to propose a pentacoordenado complex with square-shaped pyramid geometry (PBQ), with chloride ions trans-positioned in the equatorial plane of the coordinating metal sphere, with the amine occupying the apical position of the pyramid due to its strong σ-donor character. The ROMP reactions of NBE and NBD monomers using the new complex were performed under argon atmosphere as a function of the [monomer]/[Ru] molar ratio (1000, 3000, 5000, 7000 and 10000), reaction time (5, 30 and 60 min) and temperature (25 and 50 ° C). With a volume of 5 µL of ethyldiazoacetate (EDA), at 25 °C and a 5000 molar ratio of monomer for 5 min, 65% polyNBE was obtained with Mn = 0.8 x 105 and IPD equal to 1.9. The polymers obtained with NBD showed 20% yield at 25 °C for 5 min. The polymers obtained with norbornadiene showed a yield of about 20% at 25 °C for 5 min. Polymerization reactions in air atmosphere resulted in values close to those observed in argon atmosphere, suggesting that the complex presents resistance to oxidative processes caused by O2 from the ambient atmosphere. The polymerization reactions were performed in the presence of other diazocompounds benzyldiazoacetate (BDA) and tert-butyldiazolacetate (TBDA) as sources of carbenes. In order to evaluate the electronic and steric influence caused by the different R groups of these diazocompounds, it was observed that ethyldiazoacetate EDA) presented the best yield values of the isolated polymers, probably due to the balance in the steric and electronic characteristics of this diazo in front of the Ru(II) center.

Iron-catalysed carbonyl reduction, nitro reduction, formal hydroamination, and the radical alkenylation of alkyl halides have been developed. A Simple, easy-to-make, air- and moisture-stable iron(III) amine-bis(phenolate) complex catalysed the hydrosilylation of carbonyl compounds efficiently using triethoxysilane as the reducing agent. The reaction tolerated a wide range of substrates to give the corresponding alcohol products in good to excellent yields after hydrolysis of the hydrosilylated products (Scheme A1). Scheme A1. Iron-Catalysed Hydrosilylation of Carbonyl Compounds. The same catalyst was also an active catalyst for the chemoselective reduction of nitro arenes into corresponding amines using triethoxysilane as reducing agent. The method exhibited excellent chemoselectivity as other reducible functional groups such as halogen, ester, nitrile all kept unchanged during the reaction. This catalytic system was then successfully applied to the formal hydroamination of alkene to give substituted amine in synthetic useful yields under mild condition. The reaction is hypothesised to proceed through a radical intermediate (Scheme A2). Scheme A2. Iron-Catalysed Nitro Reduction and Alkene Formal Hydroamination. Finally, FeCl2-catalysed formal Heck cross-coupling has been developed between alkyl halides and styrenes. The reaction tolerated both electron-rich and electron-neutral substrates to give the products in moderate to excellent yields. Initial studies revealed that the reaction also proceeds through a radical intermediate (Scheme A3). Scheme A3. Iron-Catalysed Formal Heck Cross-Coupling of Functionalised Alkyl Halides.

This Dissertation investigates the kinetics of CO2 methanation over nickel and cobalt catalysts. Methanation was studied for both Ni/γ-Al2O3 and Co/ZrO2 catalysts, which were synthesised using an incipient wetness impregnation technique and subsequently characterised using analyses based on gas adsorption, XRD, TPR and thermogravimetry. Separately a CO hydrogenation reaction, the Fischer-Tropsch process, was modelled numerically to examine the influence of mass transfer in practical, commercial pellets of catalyst. The kinetics of methanation was investigated for Ni/γ-Al2O3 over a wide range of reactant partial pressures using a gradientless, spinning-basket reactor operated in batch mode and in a laboratory-scale, continuous fixed-bed reactor. Langmuir-Hinshelwood kinetic models were developed to represent the observed kinetics in each reactor: these models were then compared. For the batch reactor, a rate expression based the dissociation of a chemisorbed CO intermediate being the rate-limiting step was found to be consistent with the experimental results. However, results from the fixed-bed suggested that the hydrogenation of an adsorbed C atom determined the rate of reaction. These differences in the kinetics on Ni/γ-Al2O3 between the fixed-bed and batch reactors suggest that a Langmuir approach using a single, rate-determining step may not be representative across all conversions. The rate over the Co/ZrO2 catalyst was characterised in the fixed-bed reactor over a range of reactant partial pressures at temperatures between 433 K and 503 K. The rate was observed to be dependent on hydrogen partial pressure and temperature, with the rate increasing with both. Previous research has reported a wide range of values of the apparent activation energy, with a study suggesting it was sensitive to pressure. Accordingly, the apparent activation energy was investigated for pressure sensitivity over a range of pressures between 5 and 15 barg: it was found to be constant. The values determined (~88-91±8 kJ/mol) were notably consistent with those reported for CO hydrogenation on cobalt. Kinetic schemes based on Langmuir-Hinshelwood and power law equations were evaluated, with the results best described by a reaction scheme based on the carbide pathway, with a rate-determining step of CH hydrogenation. A reaction-diffusion model of the Fischer-Tropsch process in a 2-D hollow cylinder was developed and analysed across a range of Thiele moduli and the extents of error in both effectiveness factor and selectivity were quantified relative to one-dimensional sphere and slab analogues. The errors between 2-D and 1-D analogues were found to be most significant between Thiele moduli of ~0.25 and ~3. Hollow cylinder effectiveness factors were bounded by those of sphere and slab above and below Thiele moduli of ~0.75 and ~1.15 respectively for the conditions examined, with the effectiveness factors exceeding those of both sphere and slab models between these moduli. A comparison of the hollow cylindrical pellets against spheres of equivalent volume demonstrated that hollow cylinders provided improved fixed-bed performance, with improved effectiveness factors and selectivities due to the lowered diffusion lengths of the hollow cylindrical geometry.