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Carbon-Hydrogen and Carbon-Fluorine Bond Activation Promoted by Adjacent Metal Centres Open Access


Other title
Carbon-Fluorine Bond Activation
Metal-Metal Cooperitivity
Carbon-Hydrogen Bond Activation
Type of item
Degree grantor
University of Alberta
Author or creator
Slaney, Michael E
Supervisor and department
Cowie, Martin (Chemistry)
Examining committee member and department
Jaeger, Wolfgang (Chemistry)
Bergens, Steven (Chemistry)
Johnson, Samuel (Chemistry & Biochemistry)
Spyracopoulos, Leo (Biochemistry)
Buriak, Jillian (Chemistry)
Department of Chemistry

Date accepted
Graduation date
Doctor of Philosophy
Degree level
The facile cleavage of relatively inert chemical bonds followed by their functionalization into value-added products is an important goal in chemistry. Although monometallic complexes are effective at both the cleavage of inert bonds and the subsequent functionalization of the activated substrates, it is intriguing to consider the influence a second metal can have in promoting reactivity not commonly observed in monometallic systems. This dissertation explores the roles that metal-metal cooperativity and ancillary diphosphine ligands play in the selective C–H bond activation of α-olefins and C–F bond activation of fluoroolefins. Two unique bimetallic systems, bridged by bis(diphosphine) ligands, are the focal point for this study, with the first system containing the bis(diphenylphosphino)methane (dppm) ligand (Chapters 2 and 3), while the second uses the smaller, more basic bis(diethylphosphino)methane (depm) ligand (Chapters 4 and 5). We compare both ligand systems, emphasizing the steric and electronic factors, and how they influence the C–H bond activation of α-olefins and the C–F bond activation of fluoroolefins. In Chapter 2, methods for the selective C–F activation of trifluoroethylene when bridging two metal centres are reported under a variety of conditions followed by functionalization of the activated fluorocarbyl fragments through fluorine replacement by either hydrogen or a methyl group. Chapter 3 explores the different methods for fluoride-ion abstraction from bridging 1,1-difluoroethylene and tetrafluoroethylene units and the subsequent functionalization of the fluorocarbyl units produced. The different reactivities of the three fluoroolefins are described. Chapter 4 outlines the syntheses of depm-bridged complexes of Ir2, Rh2 and IrRh and initial reactivity studies involving these complexes, highlighted by the facile activation of both geminal C–H bonds of α-olefins by one compound. Finally, Chapter 5 describes the reactivity of fluoroolefins (vinyl fluoride, 1,1-difluoro-, trifluoro- and tetrafluoroethylene) with a depm-bridged Ir2 complex, with emphasis on the role of water in the activation processes, the difference in reactivity between the fluoroolefins studied, and the differences of complexes having either dppm or depm as an ancillary ligand.
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
Slaney, M. E.; Anderson, D. J.; Ferguson, M. J.; McDonald, R.; Cowie, M. J. Am. Chem. Soc. 2010, 132, 16544.Slaney, M. E.; Anderson, D. J.; Ristic-Petrovic, D.; McDonald, R.; Cowie, M. Accepted, Chem. Eur. J., Nov. 8, 2011.Slaney, M. E.; Anderson, D. J.; Ferguson, M. J.; McDonald, R.; Cowie, M. Accepted, Organometallics, Jan. 16, 2012.Slaney, M. E.; Ferguson, M. J.; McDonald, R.; Cowie, M. Accepted, Organometallics, Jan. 11, 2012.

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