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TRIFLATE and RELATED LOW OXIDATION STATE INDIUM SALTS Benjamin Cooper University of Windsor

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TRIFLATE and RELATED LOW OXIDATION STATE INDIUM SALTS Benjamin Cooper University of Windsor University of Windsor Scholarship at UWindsor Electronic Theses and Dissertations 2011 EXPLORING THE REACTIVITY OF INDIUM(I) TRIFLATE AND RELATED LOW OXIDATION STATE INDIUM SALTS Benjamin Cooper University of Windsor Follow this and additional works at: http://scholar.uwindsor.ca/etd Recommended Citation Cooper, Benjamin, "EXPLORING THE REACTIVITY OF INDIUM(I) TRIFLATE AND RELATED LOW OXIDATION STATE INDIUM SALTS" (2011). Electronic Theses and Dissertations. Paper 388. 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. EXPLORING THE REACTIVITY OF INDIUM(I) TRIFLATE AND RELATED LOW OXIDATION STATE INDIUM SALTS By Benjamin F. T. Cooper 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 2011 © 2011 Benjamin F. T. Cooper “Exploring the reactivity of indium(I) triflate and related low oxidation state indium salts” By Benjamin F. T. Cooper APPROVED BY: ______________________________________________ Dr. D. S. Richeson University of Ottawa ______________________________________________ Dr. C. G. Weisener Department of Earth and Environmental Sciences ______________________________________________ Dr. S. J. Loeb Department of Chemistry and Biochemistry ______________________________________________ Dr. R. W. Schurko Department of Chemistry and Biochemistry ______________________________________________ Dr. C. L. B. Macdonald, Advisor Department of Chemistry and Biochemistry ______________________________________________ Chair of Defense Declaration of Co-Authorship / Previous Publication I. Co-Authorship Declaration I hereby declare that this thesis incorporates material that is result of joint research, as follows: This thesis also incorporates the outcome of joint research undertaken in collaboration with Hiyam Hamaed under the supervision of Professor Robert Schurko. The collaborative work is present in Chapters 5 and 7 of the thesis. In all cases the key ideas, 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 solid state nuclear magnetic resonance spectra. I am aware of the University of Windsor Senate Policy on Authorship and I certify that I have properly acknowledged the contribution of other researchers to 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 Publication This thesis includes a book chapter and 6 original papers that have been previously published/submitted for publication in peer reviewed journals, as follows: Thesis Publication title/full citation Publication status Chapter Chapter 1 Benjamin F.T|. Cooper and Charles Published L.B. Macdonald; Mixed or Intermediate Valence Group 13 Metal Compounds. In The Group 13 Metals Aluminium, Gallium, Indium, and Thallium: Chemical Patterns and Peculiarities; Aldridge, S.; Downs, A.J.; 2011 Chapter 2 Alternative syntheses of univalent Published indium salts including a direct route from indium metal / Benjamin F.T. Cooper, and Charles L.B. Macdonald; New Journal of Chemistry, 2010, 34, 8, 1551-1555 Chapter 3 Synthesis and structure of an indium(I) Published “crown sandwich” / Benjamin F.T. Cooper, and Charles L.B. Macdonald; Journal of Organometallic Chemistry, 2008, 693, 1707-1711 iii Chapter 4 The insertion reactions of “crowned” Published indium(I) trifluoromethanesulfonate into carbon-chlorine bonds / Benjamin F.T. Cooper, Christopher G. Andrews, and Charles L.B. Macdonald; Journal of Organometallic Chemistry, 2007, 692, 13, 2843-2848 Chapter 5 Potassium cation exchange with Published “crowned” indium(I) trifluoromethanesulfonate / Benjamin F.T. Cooper, and Charles L.B. Macdonald; Main Group Chemistry, 2010, 9, 141 Chapter 6 “Crowned” univalent indium complexes Accepted for Publication as donors? Experimental and computational insights on the valence isomers of EE`X4 species / Benjamin F.T. Cooper, Hiyam Hamaed, Warren W. Friedl, Michael R. Stinchcombe, Robert W. Schurko, and Charles L.B. Macdonald; Chemistry: A European Journal, Accepted (1,4,7,10,13,16- Hexaoxacyclooctadecane)dimethyl- indium(III)trifluorosulfonate / Benjamin F.T. Cooper, and Charles L.B. Published Macdonald; Acta Cryst., 2011, E67, m233-m234 I certify that I have obtained a written permission from the copyright owner(s) to include the above published material(s) in my thesis. I certify that the above material describes work completed during my registration as graduate student at the University of Windsor. 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 This dissertation‟s primary focus is on expanding the chemistry of the unusually soluble inorganic indium(I) salt, indium trifluoromethanesulfonate (Indium triflate, InOTf). The utility of InOTf as a reagent required the development of a clean synthetic protocol in which the desired salt is produced in a reaction directly from indium metal. The ability to ligate this salt with cyclic ethers has been previously reported, however, the unique structural and chemical features observed upon tuning the crown ether cavity size are elucidated. The sandwich-like structure of the [15]crown-5 adduct is reported, and the temperature dependence of the crystalline phase is investigated. The affinity of crown ethers for alkali metals should allow a synthetic route for removal of the indium center from the ligand. Toward this end reactions of [In([18]crown-6)][OTf] with various potassium salts are reported. The ability to ligate InOTf with cyclic ethers has been found to drastically alter the reactivity of the triflate salt, specifically with respect to insertion reactions into carbon-chlorine bonds in halogenated solvents. The reactions of "crowned" InOTf complexes with CH2Cl2 and CHCl3 are reported. The mixed valent nature of E2X4 species, indium(+2) chloride for example, was used as a model for an improved synthesis of [In][EX4] salts. These salts also form crown ether complexes and produce the first new valence isomer of In2X4 observed in over 50 years. The structural features of these "crowned" species are found to depend on both the cavity size of the crown ether and the element E. Computational analyses of these complexes suggest that the covalent nature of the anion plays a role in the donor capabilities of the crowned indium(+1) fragment. v The reactivity of InOTf wth α-diimine ligands is also discussed along with preliminary structural evidence and computational analyses. The nature of both the anion and the ligand are found to have an impact on the energy and reactivity of the "lone pair" of electrons on the univalent indium center. vi ACKNOWLEDGEMENTS First and foremost I need to extend my gratitude to Chuck Macdonald for his guidance and support throughout the course of my doctorate degree. On top off all the nice things I can say about Chuck, I can add that he and his wife Inga make an excellent Mr. and Mrs. Claus. Over the years there have been many graduate students throughout the department that I would like to thank. Whether they provided fruitful discussions or necessary distractions, it helped create a great environment to be around. I would specifically like to thank Hiyam Hamaed for our collaborations. I would also like to thank the many faculty and staff members here in the Chemistry department that have helped me along the way. Whether it was helping me learn how to use an instrument, file paperwork, or helping with my GA requirements, there have been many people that have made being a part of this department enjoyable. Special thanks to Joe Lichaa for all of his help with maintenance and computer
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