This thesis describes the synthesis and application of three types of selectively functionalized mesoporous materials. In the first section, periodically ordered mesoporous organosilicas (PMOs) are prepared that have the axially chiral bidentate phosphine ligand 2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl (BINAP) embedded in the wall structure. Asymmetric hydrogenation of β-ketoesters under high-pressure hydrogen gas and hydrogen transfer reduction were carried out using Ru catalysts resulting from these materials. In the next chapter, our new methodology to selectively functionalize the internal/external surface of SBA-15, a mesoporous silica whose pore diameter is ~8 nm, by blocking the pore surface with reloaded Pluronic P123® micelles is presented. Multiple tests were attempted to validate the efficiency of the methodology including nitrogen adsorption, quantitative analysis by solid state NMRs, fluorescence measurements, elemental analysis and XPS. Eventually SS NMR proved to be the most appropriate. Finally, chapter four describes ordered organic materials in catalysis, namely star-shaped polymers containing chiral core-gels synthesized from chiral 1,1’- binaphthalene-2,2’-diol (BINOL) and 1,1’-binaphthalene-2,2’-diamine (BINAM). The kinetic resolution of 1-phenyl ethanol was carried out expecting to see differential affinity of the chiral core-gel to one enantiomer of the substrate in hydrogen transfer oxidation reaction. / Thesis (Ph.D, Chemistry) -- Queen's University, 2013-02-25 12:08:40.27
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:OKQ.1974/7827 |
| Date | 26 February 2013 |
| Creators | Seki, Tomohiro |
| Contributors | Queen's University (Kingston, Ont.). Theses (Queen's University (Kingston, Ont.)) |
| Source Sets | Library and Archives Canada ETDs Repository / Centre d'archives des thèses électroniques de Bibliothèque et Archives Canada |
| Language | English, English |
| Detected Language | English |
| Type | Thesis |
| Rights | This publication is made available by the authority of the copyright owner solely for the purpose of private study and research and may not be copied or reproduced except as permitted by the copyright laws without written authority from the copyright owner. |
| Relation | Canadian theses |
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