Physical Sciences and Mathematics Commons^™

Metal-Ligand Cooperative Catalysis And Methods For Metal Removal From Organic Transformations, John-Paul J. Bow

Electronic Thesis and Dissertation Repository

Organometallic catalysis has revolutionized the synthesis of complex organic molecules. Methods for C-C, C-X and C-H bond formation and cleavage are exploited throughout the areas of fine chemicals synthesis, with major applications for pharmaceuticals. This situation raises duel challenges: 1) high-performance catalysts for environmentally and economically sustainable synthesis and 2) efficient methods of catalyst (i.e. metal) removal must be identified. This work tackles both of these areas. The highly tunable cooperative P^R₂N^R'₂ ligands have been implemented for the first time for catalytic organic transformations. I show that [Ru(Cp)(P^tBu₂N^Bn₂)(MeCN)][PF_{6 …}

Self-Assembly And Stimuli-Responsive Properties Of Amphiphilic Self-Immolative Block Co-Polymers, Thomas Mackenzie Gungor

Electronic Thesis and Dissertation Repository

In recent years, degradable polymers have become increasingly researched for their applications in drug delivery systems, adhesives, and tissue engineering. Self-immolative polymers (SIPs) are of particular utility due to predictable end-to-end backbone depolymerization after a stimuli-responsive end-cap cleavage. There are examples of incorporating a hydrophobic SIP into an amphiphilic block-copolymer, followed by self-assembly in aqueous media forming various nanoparticle morphologies. However, their self-assembly behaviour has not been described in detail, and there are no general synthetic methods that allow for their synthesis with good control over the relative hydrophilic block ratio, the major factor controlling their morphology. This thesis presents …

Stimuli-Responsive Polymersomes And Surface Functionalized Dendrimersomes: Platforms For Biomedical Applications, J Trevor Mcintosh

Electronic Thesis and Dissertation Repository

Amphiphilic block copolymers (BCPs) and dendrimers are known to self-assemble in aqueous solution to form a number of aggregate morphologies. These different architectures are largely a function of the hydrophilic volume or weight fractions of the different components of the polymer system. One possible morphology is a vesicle, also referred to as a polymersome or dendrimersome when BCPs or dendrimers, respectively, are used. Vesicles are multi-functional, supramolecular, bilayer assemblies, whose potential for stimuli-responsiveness and surface functionalization make them promising materials for a variety of biomedical applications. This thesis demonstrates the use of UV-sensitive block copolymers forming photodegradable vesicles, as well …

Mechanistic Studies Of Donor-Acceptor Cyclopropanes, Tristan Chidley

Electronic Thesis and Dissertation Repository

Cyclopropane 1,1-diesters have been investigated as a source of donor-acceptor cyclopropanes, providing an understanding of the mechanism of reaction between these cyclopropanes and nitrosoarenes, as well as azo dicarboxylates. Cross-over experiments have been utilized to provide key pieces of experimental evidence that help generate a theoretical model of the reactions. By understanding these reactions with precision, the avenue to expand the reaction scope and develop other useful reactions is opened up. This allows the chemistry to be better utilized, providing easier access to important molecules when needed, and contributes to advancing the field of synthetic organic chemistry.

In addition, cyclobutane …

Strategies For Photochemical And Thermal Modification Of Materials, Sara Ghiassian

Electronic Thesis and Dissertation Repository

The modification of materials/surfaces is central to numerous applications ranging from opto-electronic devices to biomedical implants and drug delivery. Thus, there exists a high motivation for improving the methodologies which can be employed in order to modify surfaces in a selective and efficient fashion. One of the major goals of surface engineering is to control the chemical composition at the material interface. The fine control of the surface properties is a field of intense research as the performance of functional materials is strongly related to the processes and interactions that are occurring at the materials’ interface.

In general, the modification …

Exploring The Chemistry Of Η5-Cyclopentadienyl-Cobalt-Η4-Cyclobutadiene Containing Polymers; Synthesis, Properties, And Self-Assembly, Mahboubeh Hadadpour

Electronic Thesis and Dissertation Repository

Metal containing polymers (metallopolymers) bring together the synthetic efficiency and versatility of conventional organic polymers with unique redox, responsive, and catalytic properties of inorganic metals. Over the last decade, metallopolymers have gained increased attention because of their unique physical and chemical properties that arise from the incorporation of metal centers into a polymer. Since the first report on a metallocene-based metallopolymer in 1955, there has been growing interest in this class of material. Ferrocene-based metallopolymers represent the vast majority of metallocene containing polymers in the literature. In 1992, the Manners Group established a major milestone in the field of metallopolymers …

Design, Synthesis, And Reactivity Of Bimetallic Complexes Of Dimethylplatinum(Ii) Containing Ditopic Ligands, Matthew S. Mccready

Electronic Thesis and Dissertation Repository

This thesis describes a study of monometallic and bimetallic dimethylplatinum(II) complexes containing ditopic nitrogen donor ligands. This work details the design and synthesis of side-to-side and cofacial arranged ligands and their respective coordination chemistry. The study of the synthesis, characterization and reaction mechanisms of the various dimethylplatinum(II) complexes is outlined in detail with special emphasis focused on the reactivity of the complexes towards oxidative addition.

The ditopic ligand 6-dppd, 1,4-di(2-pyridyl)-5,6,7,8,9,10-hexahydrocycloocta[d]pyridazine, was observed to coordinate only a single equivalent of a platinum(II) center. The inability to coordinate a second equivalent, even through an assisted bridging atom, is presumed to be due …