Fluorocarbons (FCs) and their derivatives (FCDs) are heavily relied on due to their wide range of uses (e.g. solvents, surfactants, refrigerants, and pharmaceuticals). Currently, FCs and FCDs are produced on an industrial scale via energy-intensive processes, using hazardous materials. Hence, new catalytic chemical technologies are required to provide cleaner and greener synthetic routes to partially fluorinated materials. The exploration of fundamental organofluorometallic chemistry of base metals, such as nickel, has potential to advance the development of novel catalytic processes towards this end. It has been established previously that zero-valent nickel complexes have the ability to efficiently catalyze the hydrodimerization of polyfluoroalkenes. The reactivity of the intermediate polyfluoronickelacycles was found to be influenced by modifications in the ligand sphere. Furthermore, an increase in oxidation state of the central metal atom was proposed as an additional strategy to increase the reactivity of the M-RF bond. In this thesis, through variation of the ligand environment and oxidation state of nickel, we have further developed the chemistry of high-valent polyfluoronickelacycles. Synthesis and characterization (NMR, EPR, UV/Vis, IR spectroscopy and electrochemistry) of new trivalent polyfluoronickelacycles are described as well as attempts to generate the corresponding tetravalent cations. Attempts to induce nucleophilic insertion of acetonitrile into the Ni-RF bond were also investigated herein. Challenges were encountered with the isolation of the tetravalent cations due to decomposition to the corresponding divalent nickelacycle.
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:OOU./en#10393/20030 |
| Date | 26 May 2011 |
| Creators | Hunter, Nicole Marie |
| 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 | Thèse / Thesis |
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