Towards P-block Catalysts: Making Chemical Bonds on a Budget

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Institution

http://id.loc.gov/authorities/names/n79058482

Degree Level

Doctoral

Degree

Doctor of Philosophy

Department

Department of Chemistry

Supervisor / Co-Supervisor and Their Department(s)

Citation for Previous Publication

M. W. Lui, C. Merten, R. McDonald, M. J. Ferguson, Y. Xu, E. Rivard. Contrasting Reactivities of Silicon and Germanium Complexes supported by N-Heterocyclic Guanidine Ligands. Inorg. Chem. 2015, 54, 2040 – 2049., M. W. Lui, N. R. Paisley, R. McDonald, M. J. Ferguson, E. Rivard. Metal-free Dehydrocoupling of Amine-boranes by Tuneable N-Heterocyclic Imine-supported Boranes. Chem. Eur. J. 2016, 22, 2134 – 2145., N. R. Paisley†, M. W. Lui†, McDonald, R.; Ferguson, M. J.; Rivard, E. Structurally versatile phosphine and amine donors constructed from N-heterocyclic olefin units. Dalton Trans. 2016, 45, 9860 – 9870. († = equal contribution).

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Abstract

The work in this thesis describes advancements made towards developing main group catalysts and designing new ligands. N-Heterocyclic imine (NHI) ligands were used to support novel boron, silicon and germanium complexes. The new boron compounds demonstrated the ability to dehydrogenate amine-boranes and instigate their dehydrocoupling. In one case, the catalytic dehydrogenation of amine-boranes was observed. Although the synthesized silicon and germanium compounds were structurally similar, they exhibited very different reactivity under reducing conditions. The former underwent a highly unusual ligand rearrangement, while the latter formed the desired two-coordinate acyclic germylene. In addition, new olefin-based ligands featuring mixed element donors were designed and their coordination chemistry with Lewis acids BH3 and AuCl revealed different binding sites. These findings led to the isolation of a bimetallic complex that employed both donors at the same time. Finally, the preliminary photoluminescent properties of copper and gold complexes supported by the new N-heterocyclic olefin-phosphine (NHOP) ligands will be discussed.

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http://purl.org/coar/resource_type/c_46ec

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This thesis is made available by the University of Alberta Libraries with permission of the copyright owner solely for non-commercial purposes. This thesis, or any portion thereof, may not otherwise be copied or reproduced without the written consent of the copyright owner, except to the extent permitted by Canadian copyright law.

Language

en

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