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Carbon-Carbon Bond Formation and Unexpected Carbon-Hydrogen Bond Activation at Adjacent Metal Centres Open Access


Other title
carbon-carbon bond formation
adjacent metal centres
bimetallic complexes
carbon-hydrogen bond activation
Type of item
Degree grantor
University of Alberta
Author or creator
MacDougall, Tiffany J
Supervisor and department
Cowie, Martin (Chemistry)
Examining committee member and department
Semagina, Natalia (Chemical and Materials Engineering)
Heinekey, D. Michael (Chemistry)
Bergens, Steven (Chemistry)
Mar, Arthur (Chemistry)
West, Frederick (Chemistry)
Department of Chemistry

Date accepted
Graduation date
Doctor of Philosophy
Degree level
The formation of carbon–carbon (C–C) bonds is central to the transformation of small, readily available hydrocarbons into value-added products with useful chemical and physical properties. An important industrial process involving C–C bond formation is the Fischer-Tropsch (FT) process which converts carbon monoxide and hydrogen into a range of useful hydrocarbons. Although this heterogeneous process is not well understood, the importance of surface-bound, bridging methylene groups in this process is recognized. This dissertion seeks to gain a further understanding of the chemistry of bridging methylene groups. Chapter 2 of this thesis explores the formation of C–C bonds by a methylene-bridged Ir/Ru system through the coupling of methylene groups with cumulene substrates. Although C–C bond formation is observed in these complexes, we also observe unexpected multiple C–H bond activations, including the unusual activation of geminal C–H bonds in olefins. In Chapter 3, we report the C–H activation of cumulenes, conjugated dienes, and monoolefins, by the tetracarbonyl Ir/Ru complex and a mechanism is presented for these activations. The original goal of C–C bond formation is revisited in Chapters 4 and 5 as we report the reactivity of the methylene-bridged Ir/Os complex with unsaturated substrates towards hydrocarbyl-bridged complexes. This metal combination appears to be a better model for FT chemistry, owing to the strong metal–carbon bonds. The reactivity of the tetracarbonyl Ir/Os complex is also reported with unsaturated substrates (Chapter 5), as a comparison to the Ir/Ru analogue. The reactivity of the Ir/M (M = Ru, Os) systems are compared to the analogous Rh/M (M = Ru, Os) systems, describing the effects of changing the group 8 metal, the group 9 metal, or both. Throughout this thesis, we attempt to elucidate the roles of the adjacent metals in C–C bond formation and C–H bond activation.
Permission is hereby granted to the University of Alberta Libraries to reproduce single copies of this thesis and to lend or sell such copies for private, scholarly or scientific research purposes only. Where the thesis is converted to, or otherwise made available in digital form, the University of Alberta will advise potential users of the thesis of these terms. The author reserves all other publication and other rights in association with the copyright in the thesis and, except as herein before provided, neither the thesis nor any substantial portion thereof may be printed or otherwise reproduced in any material form whatsoever without the author's prior written permission.
Citation for previous publication
MacDougall, T. J.; Llamazares, A.; Kuhnert, O.; Ferguson, M. J.; McDonald, R.; Cowie, M. Organometallics 2011, 30, 952.MacDougall, T. J.; Trepanier, S. J.; Dutton, J. L.; Ferguson, M. J.; McDonald, R.; Cowie, M. Organometallics 2011, 30, 5882.MacDougall, T.J.; Ferguson, M.J.; McDonald, R.; Cowie, M. Accepted, Organometallics, January 18, 2012. Manuscript ID: om-2011-01201h.R1

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