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Permanent link (DOI): https://doi.org/10.7939/R3B122

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Stepwise Activation of E–H (E = Si, Ge) Bonds at Adjacent Rhodium and Iridium Centres Open Access

Descriptions

Other title
Subject/Keyword
Bridging-germylene
Bimetallic Activation
Bridging-silylene
Type of item
Thesis
Degree grantor
University of Alberta
Author or creator
Mobarok, Md Hosnay
Supervisor and department
Cowie, Martin (Chemistry, University of Alberta)
Examining committee member and department
Hayes, Paul (Chemistry, University of Lethbridge)
Lowary, Todd (Chemistry, University of Alberta)
Bergens, Steven (Chemistry, University of Alberta)
Semagina, Natalia (Chemical Engineering, University of Alberta)
Veinot, Jonathan (Chemistry, University of Alberta)
Department
Department of Chemistry
Specialization

Date accepted
2012-08-02T13:46:53Z
Graduation date
2012-11
Degree
Doctor of Philosophy
Degree level
Doctoral
Abstract
Transition metal-mediated E–H (E = Si, Ge) bond activation plays a pivotal role in industrially important processes, such as hydrosilylation and dehydrogenative coupling of organosilanes. Activation of these bonds by mono-metallic complexes is well studied, however, E–H bond activations in bimetallic complexes, especially complexes containing two different metals, and their subsequent reactivities, have been less well studied. This thesis probes the activation of Si–H and Ge–H bonds in a variety of organosilanes and organogermanes by bimetallic complexes involving Rh/Ir metal combination. The second and third Chapters of this thesis explore the reactivity and mechanistic details of incorporation of multiple units of silicon- (Chapter 2) and germanium-containing (Chapter 3) functionalities in dppm-bridged (dppm = Ph2PCH2PPh2) complexes of Rh/Ir via stepwise activation of Si–H and Ge–H bonds. A number of intermediates are characterized either in situ (by low-temperature NMR spectroscopy) or isolated during these transformations. The subsequent reactivity of one cationic germylene-bridged complex has also been demonstrated in Chapter 3. A synthetic protocol is outlined in Chapter 4 for the selective incorporation of two different μ-silylene units, and the influence of the substituents and π-stacking interactions on the Si---Si distance (determined by X-ray crystallography) in this series and the implications related to the nature of the Si---Si interactions are discussed. By using a similar synthetic strategy a series of (μ-silylene)/(μ-germylene) complexes have also been synthesized. Finally in Chapter 5, Si–H bond activations of silanes have been studied in a Rh/Ir complex bridged by an electronically rich and less-sterically hindered bridging ligand, depm (depm = Et2PCH2PEt2).
Language
English
DOI
doi:10.7939/R3B122
Rights
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
Mobarok, M. H.; Oke, O.; Ferguson, M. J.; McDonald, R.; Cowie, M. Inorg. Chem. 2010, 49, 11556.A version of this Chapter has been published. Mobarok, M. H.; Ferguson, M. J.; McDonald, R.; Cowie, M. Inorg. Chem. 2012, 51, 4020.Mobarok, M. H.; Ferguson, M. J.; McDonald, R.; Cowie, M. Organometallics 2012 3, 4722.

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File title: Main_content
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