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The Iron Mediated (1,5)-Homologous Michael Reaction As A Route To Spirocyclic Ring Systems., Margaret Anne. Charlton
The Iron Mediated (1,5)-Homologous Michael Reaction As A Route To Spirocyclic Ring Systems., Margaret Anne. Charlton
Electronic Theses and Dissertations
The reaction between $\gamma$-acetoxy-$\alpha,\beta$-unsaturated esters with diiron nonacarbonyl produces the $\eta\sp2$-iron tetracarbonyl complexes. Addition of a Lewis acid, such as boron trifluoride etherate, produces $\eta\sp3$-iron allyl cationic complexes. These complexes react with silyl enol ethers and silyl ketene acetals to afford the addition products. The regiochemistry is such that the addition occurs at the terminus of the allyl fragment remote from the ester function to produce $\gamma$ substitution products. The geometric stability of the iron allyl cation allows the stereochemical integrity of the double bond to remain intact during the course of the reaction. Cyclic silyl ketene acetals and silyl …
Studies Of Terminal Phosphinidene Complexes Of Zirconium., Tricia Lynn. Breen
Studies Of Terminal Phosphinidene Complexes Of Zirconium., Tricia Lynn. Breen
Electronic Theses and Dissertations
Synthetic routes to terminal phosphinidene complexes of zirconium have been investigated. The attempted generation of (Cp$\sb2$Zr=PR) in the presence of polar organic unsaturates results in insertion of the organic molecule into the Zr-P single bond of the precursor. The stabilization of the Zr=P multiple bond requires a sterically demanding substituent on phosphorus. In the absence of the required steric demands, bimolecular reactions and C-H activation of the cyclopentadienyl rings occur. However, the supermesityl substituent allows for the trimethylphosphine trapping of (Cp$\sb2$Zr=PMes*) as the stable eighteen electron adduct. (Cp$\sb2$Zr=PMes*)(PMe$\sb3$) 84 is the first stable zirconium terminal phosphinidene complex. Initial reactivity studies …
Heteroditopic Receptors., Shannon Lee. Murphy
Heteroditopic Receptors., Shannon Lee. Murphy
Electronic Theses and Dissertations
This thesis describes the study of two different pairs of heteroditopic macrocyclic ligands. The main emphasis is placed on the synthesis and characterization of the receptor:substrate complexes. In Chapter 2, the synthesis and chemistry of SOX-5 and SOX-6 are explored. The ligands contain separate thiacrown and crown ether moieties linked by an aromatic spacing unit. The two different coordination sites provide locations for the binding of a soft transition metal (Cu(I)), as well as a hard alkali metal ion (Na$\sp{+}$ or K$\sp{+}$) within the same molecule. The haptoselectivity of the ligands was studied by $\sp1$H NMR and X-ray crystallography, with …
Some Physiological Aspects Of Nitric Oxide And Peroxynitrite., Dina Marie. Francescutti
Some Physiological Aspects Of Nitric Oxide And Peroxynitrite., Dina Marie. Francescutti
Electronic Theses and Dissertations
The catalytic properties of glutathione reductase for its substrate, glutathione disulphide, were altered following exposure to 100 $\mu$M peroxynitrite. The K$\rm\sb{M}$ increased from 38 $\pm$ 2 to 80 $\pm$ 3 $\mu$M and the V$\sb{\rm max}$ decreased from 328 $\pm$ 16 to 288 $\pm$ 12 $\mu$mol min$\sp{-1}$ mg protein$\sp{-1}.$ Exposure of the enzyme to S-nitrosoglutathione or nitric oxide gas showed no significant effect on the performance of glutathione reductase. The UV-visible spectrum of glutathione reductase exhibited absorbance at approximately 428 nm which is characteristic of nitrotyrosine. The peroxynitrite induced inactivation is not observed in the presence of excess glutathione disulphide. However, …
The Design And Synthesis Of Biphenol Derived Host Molecules., Nicola Jane. Fransen
The Design And Synthesis Of Biphenol Derived Host Molecules., Nicola Jane. Fransen
Electronic Theses and Dissertations
The study of host-guest chemistry is an important new area of scientific investigation. Host molecules were designed using a rigid biphenol framework, convergent binding groups and rigid spacers capable of $\pi$-stacking. The syntheses of several of such host molecules, such as 47 and 50 containing alkyne spacers and 89 and 90 containing an aryl spacer, were completed. The synthetic pathways that lead to the formation of these macrocycles will be discussed.Dept. of Chemistry and Biochemistry. Paper copy at Leddy Library: Theses & Major Papers - Basement, West Bldg. / Call Number: Thesis1996 .F72. Source: Masters Abstracts International, Volume: 34-06, page: …
Preparation And Characterization Of Organogermanium And Organotellurium Sulfur Compounds., Jincai. Yang
Preparation And Characterization Of Organogermanium And Organotellurium Sulfur Compounds., Jincai. Yang
Electronic Theses and Dissertations
The S-alkyltrithiocarbonate(thioxanthate) derivatives, $\rm Ph\sb3Ge\lbrack S\sb2CSR\rbrack,\ Ph\sb2Ge\lbrack S\sb2CSR\rbrack\sb2,\ Ph\sb2GeX\lbrack S\sb2CSR\rbrack,\ Me\sb3Ge\lbrack S\sb2CSR\rbrack\sb2,$ and $\rm Me\sb2Ge\lbrack S\sb2CSR\rbrack\sb2$, where R = Et, i-Pr, n-Pr and n-Bu, X = Cl and Br, have been synthesized by the metatheses of $\rm R\sb2GeX\sb2$ or $\rm R\sb3GeX$ with Na of $\rm KS\sb2CSR\sp\prime$, where R = Ph and Me, R$\sp\prime$ = Et, i-Pr, n-Pr and n-Bu, X = Cl and Br. The compounds were characterized by means of NMR, IR and Raman spectroscopy. The crystal structures of $\rm Ph\sb2Ge\lbrack S\sb2CS$(i-Pr)) $\sb2$, 6, and $\rm Me\sb2Ge\lbrack S\sb2CSEt\rbrack\sb2,$ 21, were determined. The immediate environment about germanium is that of …
The Self-Assembly Of Metallosupramolecular Architectures, Jeffrey Ronald Hall
The Self-Assembly Of Metallosupramolecular Architectures, Jeffrey Ronald Hall
Electronic Theses and Dissertations
This thesis describes the design, synthesis and characterization of metallosupramolecular cleft and box-shaped molecules. These compounds are generated via the self-assembly of building block compounds; metallated thioether complexes and aronatic N-donor ligands. Chapter Two describes the synthesis and characterization of the building block compounds. Cyclometallation of the thioether ligand 1,3-bis(phenylthio-methyl)benzene (PhS$\sb2$) with (Pd(CH$\sb3$CN)$\sb4$) (BF$\sb4\rbrack\sb2$ produced the species (Pd(PhS$\sb2$)(CH$\sb3$CN)) (BF$\sb4$). By varying the S-R group, a family of compounds were synthesized each possessing different physical properties. The metallated ligands exhibited inversion of sulfur and this was studied via variable temperature $\sp1$H NMR spectroscopy. As well, several ligands of the form 1,2,4,5-tetrakis-(phenylthiomethyl)benzene …
1. Enantioselective Deprotonation Reactions Of (Arene)Tricarbonylchromium Complexes, And 2. Reductive Lithiation Of (Arene)Tricarbonylchromium Acetals., Michael John. Siwek
1. Enantioselective Deprotonation Reactions Of (Arene)Tricarbonylchromium Complexes, And 2. Reductive Lithiation Of (Arene)Tricarbonylchromium Acetals., Michael John. Siwek
Electronic Theses and Dissertations
Chapter 1. Chiral alkyllithium bases are able to selectively lithiate either the pro R or pro S ortho site of several monosubstituted $\eta\sp6$-(arene)tricarbonylchromium (0) complexes. The chiral alkyllithium bases were prepared from the corresponding chloride using the radical anion, lithium 4,4$\sp\prime$-di(tert-butyl)biphenyl (LiDBB). The base derived from 8-phenylmenthol provided the highest degree of asymmetric induction in $\lbrack\eta\sp6$-(dimethoxymethyl)benzene) tricarbonylchromium (0) with a respectable chemical yield. Chapter 2. $\eta\sp6$-(Arene)tricarbonylchromium (0) acetal complexes can be reduced at low temperatures by the radical anion, LiDBB, to generate the corresponding benzyllithium complexes. Once formed, these benzyllithium complexes can trap a variety of electrophiles to give benzyl-functionalized …
An Investigation Of Ethylene Carbonate Based, Binary Solvent Electrolyte Solutions For Lithium-Ion Batteries., Barry. Klassen
An Investigation Of Ethylene Carbonate Based, Binary Solvent Electrolyte Solutions For Lithium-Ion Batteries., Barry. Klassen
Electronic Theses and Dissertations
Mixtures of solvents are commonly used in non-aqueous lithium-ion battery electrolytes. Structures comprised of the solvents and ions determine many of the electrolyte properties. Solvation structures which could exist in the electrolyte solution include separated-solvated ions, solvent separated ion pairs, solvated contact ion pairs, and polyionic aggregates. An understanding of these solvent-ion interactions will aid in the selection of solvent mixtures. The experimental techniques that were used in this investigation were Raman scattering, conductivity measurements, and viscosity measurements. The experimental results were supplemented by quantum mechanical ab initio calculations in order to gain further insight into the solvation structures. The …
Carbamylation Of Erythrocyte Membrane Components: An In Vitro And In Vivo Study., Daniel Joseph. Trepanier
Carbamylation Of Erythrocyte Membrane Components: An In Vitro And In Vivo Study., Daniel Joseph. Trepanier
Electronic Theses and Dissertations
Cyanate exists in equilibrium with urea and in its reactive form, isocyanic acid, forms a stable adduct with protein amino groups (carbamylation). Both carbamylated hemoglobin and carbamylated plasma proteins are elevated in patients with chronic renal failure (uremia) and are believed to be responsible for some of the pathophysiological consequences of uremia. The present study focused upon an in vitro/in vivo investigation of the carbamylation of erythrocyte membrane cytoskeletal and phospholipid components. The time course binding pattern of $\rm\lbrack \sp{14}C\rbrack $ cyanate to the individual cytoskeletal membrane proteins demonstrated that spectrin and ankyrin were the most extensively carbamylated proteins, incorporating …