Browsing by Subject "chromium"
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Item Advances in Synthesis of Co- and Ter- Polycarbonates and Polyesters from Non-Petroleum Feedstocks and Kinetic Studies of Ligand Substitution from Manganese Half-Sandwich Complexes(2012-07-16) Poland, Ross RiversThis dissertation is written in two parts. The first pertains to polycarbonate and polyester synthesis using relatively benign processes. The synthesis of polycarbonates from the coupling of CO2 and epoxides catalyzed by transition metal catalysts has long been studied in the DJD group. The benefits of this process are that it utilizes comparatively benign reagents, can be performed using no extraneous solvent, and is 100% atom efficient. A method potentially useful for achieving more desirable polycarbonate properties is to produce an epoxide A/epoxide B/CO2 terpolymer, thus allowing more fine "tuning" of properties to what one may desire while simultaneously influencing relative epoxide reactivity to potentially increase catalytic turnovers. Specifically, the coupling of propylene oxide and cyclohexene oxide with CO2 to yield a random copolymer with tunable properties has been studied via a Fineman-Ross analysis. Propylene oxide was found to be incorporated into the resultant polymer chain with anywhere from 4-10 times the preference of cylcohexene oxide. Although it has been reported as early as 1969, the copolymerization of epoxides and cyclic anhydrides catalyzed by transition metal complexes to yield polyesters via a chain-growth mechanism has recently gained much attention. This robust method of polyester synthesis can utilize rather inexpensive reagents to synthesize an array of polyester products which have a wide range of Tg values (-30 degrees C ? 90 degreesC), achievable through simple monomer selection. The second part of this dissertation deals with the kinetic study of ligand substitution from manganese carbonyl metal fragments. Some time ago it was postulated that complexes of the (Cp)M(CO)2L variety undergo ligand substitution via a associative mechanism allowed by a haptotropic eta5-eta3 shift in the eta5 ligand. Through kinetic studies and theoretical modeling, an approximate activation energy barrier of ~34 kJ/mol has been calculated for the ring slip of (2,5-dimethylpyrrole)Mn to occur. Additionally, further kinetic studies were performed in which Tp, a ligand electronically similar to Cp, was compared to MnCp complexes.Item DEVELOPMENT AND MECHANISTIC STUDIES OF THE CHROMIUM TETRAMETHYLTETRAAZAANNULENE CATALYST SYSTEM FOR THE COPOLYMERIZATION OF CARBON DIOXIDE AND EPOXIDES(2010-07-14) Fitch, ShawnA prominent goal of scientists is to develop products and processes to meet the ever-growing needs of society. Today's needs include products that are economical, specialized, and made through processes with minimal impact on the environment. One such product that serves an important and widespread need is poly(bisphenol A carbonate) for its physical properties and ease of synthesis and processing. However, this polymer does not meet the growing need of being environmentally benign as production involves carcinogenic, chlorinated solvents and toxic monomers that can leach out from the polymer product. An answer to this new demand is the development of a different process for the production of polycarbonate plastics utilizing carbon dioxide and epoxides. Carbon dioxide is an attractive monomer that is cheap and nontoxic, and its utilization signifies an important contribution to counteract global greenhouse emissions. The stability of carbon dioxide has posed a significant and complex challenge towards its utilization. Epoxides are attractive since they are synthesized from a wide variety of olefins, both naturally occurring and those derived from petroleum. The exploration of catalysts to facilitate the coupling of epoxides to carbon dioxide to afford polycarbonates has been under investigation in the Darensbourg lab for fifteen years, and has lead to the development of several successful systems such as zinc bisphenoxides and chromium salens. This dissertation focuses on the development of another successful catalyst system, chromium tetramethyltetraazaannulene, and further elucidation of the mechanism by which polycarbonates are formed. Herein, aspects of the copolymerization process using this system will be discussed in detail, such as cocatalyst and pressure dependence, catalyst derivatization, and kinetic and mechanistic investigations. The end result of these investigations is the development of the most active chromium-based catalyst for the copolymerization of cyclohexene oxide and carbon dioxide and a better understanding of how the copolymer product is produced.Item I. Studies on the Metal-Catalyzed Cycloadditions of Isocyanates and Unsaturated Systems and II. Chromium-Catalyzed Synthesis of 1,3-Butadienes via (Silylmethyl)allenes(2011-10-21) Duran Galvan, MariaMetal-catalyzed cycloadditions of alkynes with isocyanates or nitriles are valuable tools for the synthesis of complex carbocycles and heterocycles. Although this transformation has been studied for over three decades, the cyclizations of disocyanates with 1,3-dienes or allenes are not known and the asymmetric cycloadditions of isocyanates are scarce. To expand the scope of these powerful reactions, we studied the semi-intramolecular metal-catalyzed cycloaddition of several unsaturated systems with isocyanates. Our results show that further work in this area is needed to suppress the formation of undesired homo-coupled adducts and obtain the bicyclic products in a more efficient manner. 1,3-butadienes are versatile building blocks in organic synthesis. Therefore, it is our interest to develop an efficient method for their preparation making 1,3-butadienes more available for the organic chemist. A number of methods are known for the synthesis of these compounds, but the majority of them present problems such as poor regioselectivity, low atom economy, or require the use of toxic or non-readily available reagents. In order to develop a more effective synthesis, we employed (allenylmethyl)silanes as intermediates for the preparation of 1,3-butadienes utilizing (4-bromobut 2-ynyl)trimethylsilane as a diene equivalent. A Nozaki-Hiyama-Kishi type transformation was used for the highly regioselective preparation of (trimethylsilyl)methylallenic alcohols from aldehydes and ketones. In addition, several tridentate bis(oxazolinyl)carbazole ligands were synthesized and used for the enantioselective synthesis of allenic alcohols. Carbazole ligands synthesis was achieved by the Suzuki coupling of carbazoles with different boronic acids followed by carbonylative amidation and cyclization. We report an efficient new method for the desilylation of allenic alcohols providing a variety of secondary and tertiary 1,3-butadienylcarbinols. Furthermore, our interest in extending this methodology led us to the discovery of a novel synthesis of 2-aminomethyl-1,3-dienes from N-tosyl imines.Item Impact of the ligands on linear trimetal chains(Texas A&M University, 2004-09-30) Lei, PengIncreasing attention has been given to the preparation and study of compounds with linear chains of metal atoms surrounded by four ligands. The majority of linear trimetal complexes are supported by dpa, the anion of dipyridylamine, having the general formula M3(dpa)4X2, where X is typically a monoanion. It has been shown that the behavior of the trinuclear system is far more complicated than might have been expected. Specifically, both symmetrical and unsymmetrical chains can occur and the interpretation of the magnetic properties of certain compounds has been a challenging task. Present in this dissertation is the bulk of work completed on an exploration of syntheses and characterizations of linear trichromium and trinickel compounds with different types of tridentate ligands. These ligands include 2,6-bis(phenylamino)pyridine,H2BPAP, (the corresponding dianion of this is denoted by BPAP) and a set of five unsymmetrical formamidines with different organic substituents ranging from strong electron-donating groups, such as -OCH3, to electron-withdrawing groups, e.g., F. Ligands impact on the trimetal chain in various ways. In the case of the M3(BPAP)42- ions, there are no axial interactions because these anionic species do not attract electron donating ligands. Thus they have properties which are different from those of M3(dpa)4X2 molecules. Most notably, the Ni3(BPAP)42- ion is diamagnetic and all three nickel ions can be described as square-planar, low-spin NiII centers. ivWhen unsymmetrical formamidines are used to support linear trichromium chains with a Cl anion at each end, the separation between terminal chromium atoms is significantly longer (ca. 0.15 - 0.25) than those in trichromium compounds reported earlier. Moreover, the unsymmetrical formamidinates tend to support symmetrical trichromium chains, while the rest of the known tridentate ligands typically yield unsymmetrical Cr36+ chains. The synthesis and structural studies of trinickel compounds with unsymmetrical formamidines are also presented.Item Remediation of chromium(VI) in the vadose zone: stoichiometry and kinetics of chromium(VI) reduction by sulfur dioxide(Texas A&M University, 2004-11-15) Ahn, MinImmobilization and detoxification of chromium in the vadose zone is made possible by the existence of an effective reductant, SO2, that exists in a gaseous form at room temperature. Experimental studies were designed to characterize stoichiometry and kinetics of chromium reduction both in aqueous solutions at pH values near neutrality and in soil. First, batch experiments and elemental analyses were conducted to characterize the stoichiometry and kinetics of Cr(VI) reduction in water. The stoichiometric ratio of S(IV) removed to Cr(VI) removed ranged between 1.6 and 1.8. The overall reaction is believed to be the result of a linear combination of two reactions in which dithionate is an intermediate and sulfate is the stable oxidized product. The reaction was also rapid, with the half-time of about 45 minutes at pH 6 and about 16 hours at pH 7. A two-step kinetic model was developed to describe changes in concentrations of Cr(VI), S(IV), and S(V). Nonlinear regression was applied to obtain the kinetic parameters. The rate of reaction was assumed to be second-order with respect to [Cr(VI)] and first-order with respect to [S(IV)], and [S(V)]. The values for the rate coefficient for the first reaction (k1) were found to be 4.5 (?10%), 0.25 (?9.4%) (mM-2h-1) at pH 6 and 7, respectively. The values of the rate coefficient for the second reaction (k2) were 25 (?29%), 1.1 (? 30%) (mM-2h-1) at pH 6 and 7, respectively. The reaction rate decreased as pH increased. Experiments showed that the rate at pH 7 was lower than that at pH 6 by one order of magnitude. Second, batch experiments and elemental analyses were conducted to characterize the stoichiometry and kinetics of Cr(VI) reduction in soil. The stoichiometric ratio of S(IV) removed to Cr(VI) removed was almost 2, which is slightly higher than that for the reaction in water. This higher value may be due to S(IV) oxidation by soil-derived Fe(III). The reaction was rapid, with the half-time less than 2 minutes, which is faster than in water. The rate coefficients, k1 and k2, were 22 (?41%) and 13 (?77%) (M-2h-1), respectively.Item Structural and mechanistic studies into the copolymerization of carbon dioxide and epoxides catalyzed by chromium salen complexes(Texas A&M University, 2006-08-16) Mackiewicz, Ryan MichaelThe ability to utilize cheaper starting materials in the synthesis of commercially important materials has been a goal of scientists since the advent of the chemical industry. The ideal situation would be one in which by combining the correct proportions of hydrogen, nitrogen, carbon and oxygen that virtually anything from simple sugars to complex polymers could be produced. Unfortunately, such processes are flights of fancy often reserved for movies and television shows. On a more realistic level, the utilization of simple molecules and a transition metal catalyst has been a process that industry has exploited for many years. The most easily identifiable process is that for polyolefin production, that employs homopolymerization of simple monomers such as ethylene and catalysts ranging from Ziegler-Natta to metallocene type catalysts. On a more difficult level copolymerization reactions require a delicate balance between two competing reactions and as a result these reactions have been much less successful. For over a decade now the Darensbourg Research Laboratories have focused on utilizing another simple molecule: carbon dioxide. Carbon dioxide is a cheap, inert, nontoxic starting material that appears to be an ideal monomer. Although simplistic, CO2 is also very stable and its utilization in polymerization reactions have proven to be quite complex. In order for us to facilitate these reactions we employ both a transition metal catalyst and a comonomer. Epoxides act as an effective comonomer because the thermodynamic energy gained from breaking the strained three membered epoxide ring overcomes the stability of CO2 and allows the copolymerization reaction to occur. We have demonstrated a great deal of success with this process, most of which will be mentioned throughout this report. The majority of this dissertation will detail our use of salen complexes to optimize this copolymerization process, in order to further the use of CO2 as a viable source of C1 feedstock. Herein, I will illustrate how we have obtained more than a 100 fold increase in the rate of polymer formation as well as detailed mechanistic data that will provide a basis for future catalyst design studies.