published_or_final_version / Chemistry / Master / Master of Philosophy

Thesis (Ph. D.)--Chemistry and Biochemistry, Georgia Institute of Technology, 2009. / Committee Chair: Weck, Marcus; Committee Member: Breedveld, Victor; Committee Member: Bunz, Uwe; Committee Member: Liotta, Charles; Committee Member: Marder, Seth; Committee Member: Srinivasarao, Mohan. Part of the SMARTech Electronic Thesis and Dissertation Collection.

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

A unifying theme of the chemistry presented is the synthesis, study, and application of a novel N-heterocyclic carbenes. Pursuit of these materials has resulted in new advances in carbene structure and bonding, the discovery of highly-efficient reactions, and the development of new polymers with unusual properties. / text

published_or_final_version / Chemistry / Master / Master of Philosophy

The primary goal of this study is to develop novel metal catalyzed multicomponent reaction methods to generate imidazoles and their derivatives. This is directed towards the assembly of poly-substituted imidazoles, imidazolones and imidazole-containing pi-conjugated polymers. These products are generated in one-pot from such basic components as imines, acid chlorides, carbon monoxide, and/or organostannanes, via the use of palladium catalysis. / In Chapter 2, the design of a new palladium catalyzed synthesis of highly substituted imidazoles from imines and acid chlorides is described. This reaction involves the palladium catalyzed generation of 1, 3-oxazolium-5-oxides (Munchnones); which are trapped with N-tosyl substituted imines via a 1, 3 dipolar cycloaddition reaction to form the final products. Overall, this provides a one step method to assemble imidazoles from imines and acid chlorides with excellent regiochemical control. The versatility of this process is demonstrated by the assembly of diversely substituted imidazoles, including those with aryl, alkyl, heterocyclic and vinyl substituents. / Chapter 3 describes a new, palladium catalyzed, five component coupling of imines, chloroformates, organotin reagents, carbon monoxide and ammonium acetate to form imidazolones. The key step in this process is the efficient formation of ketocarbamates via the carbonylative cross coupling type reaction of imines, chloroformates and organostannanes. These products can be easily converted into imidazolones via a cyclocondensation with ammonium acetate. / The synthesis of pi-conjugated imidazole-containing polymers is described in Chapter 4. This process is designed based upon our previous studies on palladium catalyzed multicomponent synthesis of imidazoles, developed in Chapter 2. It is shown that bifunctional monomers such as di-imines, di-acid chlorides and di-N-tosylimines can be coupled together to assemble pi-conjugated imidazole-containing oligomers and polymers utilizing this same palladium catalyzed reaction. This approach was used to create a novel library of conjugated imidazole polymers. By modifying the substituents on the polymer structures, the UV-vis absorbance and fluorescence excitation/emission spectra of these compounds are varied over a range of 150 nm. / In Chapter 5, the palladium catalyzed multicomponent polymerization is discussed in more detail. This includes the analysis of the end groups on the polymer backbone, as well as mechanistic studies into how the polymerization is terminated. These results suggest that the sulfinate anion liberated upon N-tosylimine cycloaddition may be non-innocent in this polymerization, and its presence could lead to termination of the growing polymer chain.

<p>Development in the field of materials science is propagated by the synthesis of polynuclear metal-containing complexes, that exhibit enhanced chemical and physical properties. This thesis describes the synthesis of new metal-containing linear polymers and dendritic molecules.</p> <p>Chapter 1 presents an overview of the field of metal-containing polymers, with particular attention to the synthesis of polymers via condensation polymerisation. This review includes the various types of metal-containing condensation polymers and the applications of these materials, where available. This discussion is followed by a brief summary of metal-containing dendrimers, which includes a concise description of their structure and applications in general.</p> <p>There are two routes to preparing metal-containing polymers. Chapter 2 describes the synthesis of three bifunctional organometallic monomers, of the general type [M]-O-{2,6-(CH2OH)2-4-CH3-C6H2}, where [M] represents the various metal-containing moieties, (&eta / 5-C5H5)(CO)2 Fe(CH2)3 (25), (&eta / 5-C5H4-CH2CH2CH2-)Re(CO)3 (26) and Fpdendr (27). These monomers were prepared using 2,6-bis(hydroxymethyl)-p-cresol as the key reagent. The monomers were used in classical polycondensation reactions with terephthaloyl chloride using ambient temperature solution techniques. This yielded new low molecular weight oligomeric polyesters, that were characterised using FTIR and 1HNMR spectroscopy, differential scanning calorimetry, thermogravimetric analysis and sizeexclusion chromatography.</p> <p>In Chapter 3, an alternate route to metal-containing polymers is described. In this case, bifunctional organic monomers were polymerised to give preformed organic polymers. Two types of organic polymers were prepared, viz. polyesters (with pendant vinyl moieties) and polyimines (with &alpha / -diimine units along the polymer backbone). Functionalisation of these preformed organic polymers with various metal sources was attempted. Hydrozirconation reactions of the vinyl polyesters with Schwartz&rsquo / s reagent, Cp2Zr(H)Cl, were attempted and were largely unsuccessful. Competing reactions with the ester functionality prevailed, preventing the desired reaction. Reaction of the polyimines with PdCl2(COD) yielded insoluble, intractable metal-containing oligomers. Partial characterisation of the complexes is described.</p> <p>The synthesis of new poly(propylene imine) iminopyridyl metallodendrimers is described in Chapter 4. Schiff-base condensation reaction of the commercially available DAB dendrimers with 2-pyridinecarboxaldehyde, gave the dendrimers 51, 52, and 53, with four, eight and sixteen pyridylimine functionalities respectively on the periphery. Successful complexation reactions with PdCl2(COD), PtCl2(COD) and CuCl2 produced the corresponding metal-containing dendrimers, with either PdCl2 (54, 55, 56), PtCl2 (57) or CuCl2 (58) moieties bound on the periphery. The metallodendrimers were insoluble in the more common organic solvents, and were characterised by IR and 1H-NMR spectroscopy and microanalysis where possible. Dendrimers with salicylaldiminato ligands on the periphery were prepared by reacting the DAB dendrimers with salicylaldehyde. These ligands were reacted with various metal acetates in an attempt to prepare new metalcontaining salicylaldimine dendrimers. This work yielded either paramagnetic metal complexes or insoluble, intractable compounds.</p> <p>Chapter 5 describes the applications of the catalyst precursors (54, 55, 56, 57, 58), discussed in Chapter 4, in the polymerisation of ethylene and the use of complexes 54 and 55 as Heck cross-coupling catalyst precursors. The complexes all showed catalytic activity toward ethylene polymerisation. A discussion of their activity, the polyethylene molecular weight and microstructure is presented in this chapter. The precursors 54 and 55 are also effective catalysts in the Heck reactions, coupling iodobenzene with methyl acrylate, styrene and 1-octene in high conversions.</p> <p>General conclusions are given in Chapter 6.</p>

<p>Development in the field of materials science is propagated by the synthesis of polynuclear metal-containing complexes, that exhibit enhanced chemical and physical properties. This thesis describes the synthesis of new metal-containing linear polymers and dendritic molecules.</p> <p>Chapter 1 presents an overview of the field of metal-containing polymers, with particular attention to the synthesis of polymers via condensation polymerisation. This review includes the various types of metal-containing condensation polymers and the applications of these materials, where available. This discussion is followed by a brief summary of metal-containing dendrimers, which includes a concise description of their structure and applications in general.</p> <p>There are two routes to preparing metal-containing polymers. Chapter 2 describes the synthesis of three bifunctional organometallic monomers, of the general type [M]-O-{2,6-(CH2OH)2-4-CH3-C6H2}, where [M] represents the various metal-containing moieties, (&eta / 5-C5H5)(CO)2 Fe(CH2)3 (25), (&eta / 5-C5H4-CH2CH2CH2-)Re(CO)3 (26) and Fpdendr (27). These monomers were prepared using 2,6-bis(hydroxymethyl)-p-cresol as the key reagent. The monomers were used in classical polycondensation reactions with terephthaloyl chloride using ambient temperature solution techniques. This yielded new low molecular weight oligomeric polyesters, that were characterised using FTIR and 1HNMR spectroscopy, differential scanning calorimetry, thermogravimetric analysis and sizeexclusion chromatography.</p> <p>In Chapter 3, an alternate route to metal-containing polymers is described. In this case, bifunctional organic monomers were polymerised to give preformed organic polymers. Two types of organic polymers were prepared, viz. polyesters (with pendant vinyl moieties) and polyimines (with &alpha / -diimine units along the polymer backbone). Functionalisation of these preformed organic polymers with various metal sources was attempted. Hydrozirconation reactions of the vinyl polyesters with Schwartz&rsquo / s reagent, Cp2Zr(H)Cl, were attempted and were largely unsuccessful. Competing reactions with the ester functionality prevailed, preventing the desired reaction. Reaction of the polyimines with PdCl2(COD) yielded insoluble, intractable metal-containing oligomers. Partial characterisation of the complexes is described.</p> <p>The synthesis of new poly(propylene imine) iminopyridyl metallodendrimers is described in Chapter 4. Schiff-base condensation reaction of the commercially available DAB dendrimers with 2-pyridinecarboxaldehyde, gave the dendrimers 51, 52, and 53, with four, eight and sixteen pyridylimine functionalities respectively on the periphery. Successful complexation reactions with PdCl2(COD), PtCl2(COD) and CuCl2 produced the corresponding metal-containing dendrimers, with either PdCl2 (54, 55, 56), PtCl2 (57) or CuCl2 (58) moieties bound on the periphery. The metallodendrimers were insoluble in the more common organic solvents, and were characterised by IR and 1H-NMR spectroscopy and microanalysis where possible. Dendrimers with salicylaldiminato ligands on the periphery were prepared by reacting the DAB dendrimers with salicylaldehyde. These ligands were reacted with various metal acetates in an attempt to prepare new metalcontaining salicylaldimine dendrimers. This work yielded either paramagnetic metal complexes or insoluble, intractable compounds.</p> <p>Chapter 5 describes the applications of the catalyst precursors (54, 55, 56, 57, 58), discussed in Chapter 4, in the polymerisation of ethylene and the use of complexes 54 and 55 as Heck cross-coupling catalyst precursors. The complexes all showed catalytic activity toward ethylene polymerisation. A discussion of their activity, the polyethylene molecular weight and microstructure is presented in this chapter. The precursors 54 and 55 are also effective catalysts in the Heck reactions, coupling iodobenzene with methyl acrylate, styrene and 1-octene in high conversions.</p> <p>General conclusions are given in Chapter 6.</p>

Includes bibliographical references / xi, 228 leaves : ill ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Depts. of Physical and Inorganic Chemistry and Chemical Engineering, 1993

Thesis (Ph.D.)--Chemistry and Biochemistry, Georgia Institute of Technology, 2008. / Committee Chair: Boris Mizaikoff; Committee Member: Andrew Lyon; Committee Member: Ching-Hua Huang; Committee Member: David Collard; Committee Member: Facundo M. Fernandez.