The use of transition metal catalysts - either homogeneous (discrete well-defined metal complexes) or heterogeneous (more poorly-defined metal surfaces) - play an important role in the transformations of small substrates into larger, value-added compounds. Although heterogeneous catalysts have the greater industrial applicability, there has been enormous interest in homogeneous transition metal systems for effecting selective transformations of small substrate molecules. The bulk of these homogeneous systems are mononuclear. Perhaps surprisingly, very little research has focuses on systems with adjacent metal centres. Binuclear systems possess adjacent metals that may interact and possibly lead to transformations not observed in monometallic systems. It is this opportunity for adjacent metal involvement in substrate activation that is the focus of this dissertation. the goal of this research is to gain an increased understanding of metal-metal cooperativity and adjacent metal involvement in substrate transformations; how can adjacent metal involvement lead to substrate activation not seen in monometallic counterparts, and what role does each metal play in these interactions, particularly when the two metals are different.
Throughout this dissertation examples of transformation unique to systems with at least two metals are presented and examined with a particular focus on the roles of the two metals and any associated binding modes in these transformations. In addition, by comparing the RhOs, RhRu and IrRu systems, the influence of metal substitution is also examined. For example, diazoalkane activation and C-c bond formation promoted by the Rh-based systems is investigated, the roles of the adjacent metals of the IrRu system in the conversion of methylene groups to oxygenates is examined, and the unusual geminal C-H bond activation of olefinic substrates is explored.
Overall, the work presented within this thesis adds to the growing understanding of adjacent metal cooperativety, leading us toward a more rational approach to the design of homogeneous homo- and heterobimetallic catalysts, heterogeneous catalyst and nanoparticle catalysts for selective substrate transformations.
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:AEU.10048/745 |
| Date | 11 1900 |
| Creators | Samant, Rahul G. |
| Contributors | Cowie, Martin (Chemistry), Bergens, Steven (Chemistry), Wasylishen, Roderick (Chemistry), Buriak, Jillian (Chemistry), Choi, Phillip (Chemical and Material Engineering), Emslie, David (Chemistry, McMaster University) |
| Source Sets | Library and Archives Canada ETDs Repository / Centre d'archives des thèses électroniques de Bibliothèque et Archives Canada |
| Language | English |
| Detected Language | English |
| Type | Thesis |
| Format | 4257519 bytes, application/pdf |
| Relation | Samant, R. G.; Graham, T.W.; Rowsell, B.D.; Mcdonald, R.; Cowie, M. Organometallics 2008, 27, 3070, Samant, R.G.; Trepanier, S.J.; Wigginton, J.R.; Xu, L.; Berenstiel, M.; McDonald, M.; Ferguson, M.J.; Cowie, M. Organometallics, 2009, in press |
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