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Stabilization and Reactivity of Low Oxidation State Indium Compounds University of Windsor Scholarship at UWindsor Electronic Theses and Dissertations Theses, Dissertations, and Major Papers 2013 Stabilization and Reactivity of Low Oxidation State Indium Compounds Christopher Allan University of Windsor Follow this and additional works at: https://scholar.uwindsor.ca/etd Recommended Citation Allan, Christopher, "Stabilization and Reactivity of Low Oxidation State Indium Compounds" (2013). Electronic Theses and Dissertations. 4939. https://scholar.uwindsor.ca/etd/4939 This online database contains the full-text of PhD dissertations and Masters’ theses of University of Windsor students from 1954 forward. These documents are made available for personal study and research purposes only, in accordance with the Canadian Copyright Act and the Creative Commons license—CC BY-NC-ND (Attribution, Non-Commercial, No Derivative Works). Under this license, works must always be attributed to the copyright holder (original author), cannot be used for any commercial purposes, and may not be altered. Any other use would require the permission of the copyright holder. Students may inquire about withdrawing their dissertation and/or thesis from this database. For additional inquiries, please contact the repository administrator via email ([email protected]) or by telephone at 519-253-3000ext. 3208. STABILIZATION AND REACTIVITY OF LOW OXIDATION STATE INDIUM COMPOUNDS By Christopher J. Allan A Dissertation Submitted to the Faculty of Graduate Studies Through Chemistry and Biochemistry In Partial Fulfillment of the Requirements for The Degree of Doctor of Philosophy at the University of Windsor Windsor, Ontario, Canada 2013 ©2013 Christopher J. Allan Declaration of Co-Authorship / Previous Publications I. Declaration of Co-Authorship This thesis incorporates the outcome of joint research undertaken in collaboration with Hugh Cowley under the supervision of Jeremy Rawson. The collaborative work is present in Chapter 4 of the thesis. In all cases, primary contributions, experimental designs, data analysis, and interpretation were performed by the author and the contribution of the co- authors was primarily through the provision of electron paramagnetic resonance spectroscopy. I am aware of the University of Windsor Senate Policy on Authorship and I certify that I have properly acknowledged the contribution of the other researchers in my thesis, and have obtained written permission from each of the co-author(s) to include the above material(s) in my thesis. I certify that, with the above qualification, this thesis, and the research to which it refers, is the product of my own work II. Declaration of Previous Publications This thesis includes a summarized version of a book chapter as well as an original manuscript that have been previously submitted for publication in peer reviewed journals, as summarized below: Citation Status Chapter 1 Christopher J. Allan, Charles, L B. Macdonald; Low Accepted Coordinate Main Group Centers - Group 13 in Comprehensive Inorganic Chemistry II; Jan Reedijk, Kenneth Poeppelmeier, 2013. Chapter 4 Non-Innocent Ligand Effects on Low Oxidation State Accepted Indium Complexes; Christopher J. Allan, Benjamin F. T. Cooper, Hugh J. Cowley, Jeremy M. Rawson, and Charles L. B. Macdonald. Chemistry - A European Journal, 2013. I certify that I have obtained written permission from the aforementioned publishers to include said work in this dissertation. I certify that the work contained in this document was completed during my registration as a graduate student at the University of Windsor. iii I declare that, to the best of my knowledge, my thesis does not infringe upon anyone’s copyright nor violate any proprietary rights and that any ideas, techniques, quotations, or any other material from the work of other people included in my thesis, published or otherwise, are fully acknowledged in accordance with the standard referencing practices. Furthermore, to the extent that I have included copyrighted material that surpasses the bounds of fair dealing within the meaning of the Canada Copyright Act, I certify that I have obtained a written permission from the copyright owner(s) to include such material(s) in my thesis. I declare that this is a true copy of my thesis, including any final revisions, as approved by my thesis committee and the Graduate Studies office, and that this thesis has not been submitted for a higher degree to any other University or Institution. iv Abstract The work described herein focuses on the chemistry of low oxidation state indium salts. Indium in its +1 oxidation state is electron rich, as it possesses a “lone pair” of electrons which are capable of undergoing further chemistry, such as oxidative addition and transition metal ligation. One of the main benefits of In(I) compounds is that they are amphoteric and thus capable of acting as both a Lewis acid as well as a Lewis base. One of the major drawbacks in the field of In(I) chemistry, however, is a lack of convenient starting materials. The In(I) halides have very poor solubility in non-donor solvents and readily decompose in the presence of strong donor molecules. The addition of acyclic polyethers to a series of In(I) (and III) salts very rarely resulted in decomposition. Their effect on solubility is investigated and reported. A more soluble indium(I) salt is indium trifluoromethanesulfonate (indium triflate, InOTf). This salt is significantly more stable than its halide counterparts, however it is sometimes too inert and does not react at all. It has been previously reported that the addition of crown ether ligands increase the reactivity of the metal centre and can cause oxidative addition into carbon-chlorine bonds. The effects of various destabilizing ligands is discussed and a computational investigation provides insight into the electronic stability of these ligated systems. The reactivity with InOTf with “non-innocent” α-diimine (DAB) ligands is also investigated. These ligands are capable of undergoing redox chemistry and generating ambiguous metal oxidation states. Substitution patterns on DAB ligands were found to play a major role in the reactivity of InOTf as shown by X-ray crystallography, EPR spectroscopy, cyclic voltammetry and computational analysis. v Acknowledgements First and foremost, I would like to extend my gratitude towards my supervisor, Chuck Macdonald. He has been an excellent source of information, advice, and guidance and has always been more than willing to share his wisdom (both in and outside of chemistry). Thank you for four great years. There have been many students who have come and gone over the years who have made the time spent here memorable. I would like to thank Jill, Heather, Ben, Greg, Meghan, Raj, Steph, Jenn, and “Shmala”. The fun we had with wheely chairs, practical jokes involving bubble wrap, sprinkles, and the starfish, have all made the “MacJohnson” office a fun place to work. I would also like to thank Martin for his volunteer work in the lab (although he never remembered to add a stir bar to the flask). I would like to thank the faculty and staff in the chemistry department for their help and guidance along the way, including committee members Jim Green and Jeremy Rawson who have been more than willing to answer my burning questions. Special mention goes to Una for letting me borrow equipment/glassware from the undergraduate labs. Thank you to my family for their support over the years. Even though they may not fully understand what I’ve accomplished, they can still give anyone who is curious a “Three Minute” summary. Finally I would like to thank my external committee members Michael Hill and Maria Cioppa for reading my thesis, as well as the government of Ontario and the University of Windsor for funding. vi Table of Contents Declaration of Previous Publications........................................................................... iii Abstract....................................................................................................................... v Acknowledgements...................................................................................................... vi List of Tables............................................................................................................... ix List of Figures.............................................................................................................. x List of Schemes............................................................................................................ xiii Glossary of Terms........................................................................................................ xiv Chapter 1: Introduction................................................................................................ 1 1.1 Oxidation State vs Valence State vs Coordination Number.................................. 1 1.2 Nitrogen-based Ligands......................................................................................... 5 1.3 Carbon-based Ligands........................................................................................... 23 1.4 Chalcogen-based Ligands...................................................................................... 41 1.5 Conclusions............................................................................................................ 45 1.6 References.............................................................................................................. 47 Chapter 2: Experimental and Theoretical Insight into the
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