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Utilizing Phosphorus(I) Methods Towards Phosphorus(III) Heterocycles and Phosphorus(I) Macromolecules Gregory Farrar University of Windsor

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Utilizing Phosphorus(I) Methods Towards Phosphorus(III) Heterocycles and Phosphorus(I) Macromolecules Gregory Farrar University of Windsor University of Windsor Scholarship at UWindsor Electronic Theses and Dissertations 2012 Utilizing Phosphorus(I) Methods Towards Phosphorus(III) Heterocycles and Phosphorus(I) Macromolecules Gregory Farrar University of Windsor Follow this and additional works at: http://scholar.uwindsor.ca/etd Recommended Citation Farrar, Gregory, "Utilizing Phosphorus(I) Methods Towards Phosphorus(III) Heterocycles and Phosphorus(I) Macromolecules" (2012). Electronic Theses and Dissertations. Paper 389. 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. Utilizing Phosphorus(I) Methods Towards Phosphorus(III) Heterocycles and Phosphorus(I) Macromolecules By Gregory Farrar 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 2012 © 2012 Gregory Farrar Utilizing Phosphorus(I) Methods Towards Phosphorus(III) Heterocycles and Phosphorus(I) Macromolecules by Gregory Farrar APPROVED BY: Dr. T. Baumgartner, External Examiner University of Calgary Dr. D. Northwood Department of Mechanical, Automotive & Materials Engineering Dr. Z. Wang Department of Chemistry & Biochemistry Dr. S. Loeb Department of Chemistry and Biochemistry Dr. C. Macdonald, Advisor Department of Chemistry and Biochemistry Dr. X. Yuan, Chair of Defense Department of Computer Science March 23, 2012! Declaration of Co-Authorship/Previous Publication I. Co-Authorship Declaration Some of the material contained within this document has been previously published in peer-reviewed journals. I acknowledge my supervisor Dr. Charles L. B. Macdonald as a co-author in all work and he has made significant contributions in all aspects of my research. Jonathon Dube and Stephanie Kosnik assisted in collection of raw data for Chapters 2 and 3 respectively. Dr. Benjamin Cooper performed all of the X-ray crystallography studies and was responsible for the refinement of the structures. II. Declaration of Previous Publication This thesis includes one original paper that has been previously submitted for publication in a peer reviewed journal, as follows: Thesis Chapter Publication title/full citation Publication Status Chapter 2 A Convenient Method for the Preparation of Published N-Heterocyclic Bromophosphines: Excellent Precursors to the Corresponding N- Heterocyclic Phosphenium Salts/J. W. Dube, G. J. Farrar, E. L. Norton, K. L. S. Szekely, B. F. T. Cooper, C. L. B. Macdonald, Organometallics 2009, 28, 4377-4384. Chapter 4 Low Valent Chemistry: An Alternative In Progress Approach to Phosphorus-Containing Macromolecules/G. J. Farrar, B. F. T. Cooper, E. L. Norton, B. D. Ellis, C. L. B. Macdonald. I certify that I have obtained a written permission from the copyright owner(s) to include the above published material 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. ! iii! Abstract The oxidation state of an atom provides details into the number of electrons associated with it, as well as the chemistry of the atom. Phosphorus can exhibit a range of oxidation states such as; +1, +3, and +5. One of the main focuses of my research is to utilize phosphorus in the electron-rich +1 oxidation state to produce neutral P(I)-containing complexes that are analogous to polyphosphazenes. We have extended the class of P(I)-containing complexes from small molecules to the production of oligomers. Our work is novel in that we have found a general method that allows us to partially or completely substitute the nitrogen sites to form oligomers that are isoelectronic to that of the polyphosphazene and that will have different properties than the parent polymers. Our method is the first, and to date only, method that can produce such materials and the ease and generality of the approach suggests excellent developments in the near and distant future. Over the last two decades, N-heterocyclic phosphines have been an important class of compounds that has helped shape the development of modern main group chemistry. There have been numerous synthetic attempts to generate these species but usually involve harsh reaction conditions, long reaction times, multiple byproducts, or contain RedOX active anions. Herein, we have demonstrated the clean and spontaneous approach to generate N-heterocyclic phosphines in a high yielding, one-pot fashion. We have also established that the resulting bromophosphines have shown to be useful reagents for the generation of the corresponding N-heterocyclic phosphenium salts by several common methods of anion abstraction or metathesis reactions. We have also undertaken the task of generating new phosphorus containing heterocycles using ! iv! alternative ligands that include oxygen and sulfur elements. ! v! fam·i·ly: any group of persons closely related by blood, as parents, children..etc. This thesis is dedicated to my family, their support has made my goal achievable. ! vi! Acknowledgements Most importantly I would like to thank Dr. Macdonald. He has not only taught me an incredible amount of chemistry, he has also been a significant influence in my life. Chuck always found the time to talk about chemistry and life, his interest and concern for my family has truly been heartwarming. I would also like to thank my fellow Macdonald Group members, especially Benjamin Cooper. Ben helped make my time in Windsor bearable, and sometimes even enjoyable. In addition, I would like to thank Chris and Steph for our various office conversations and Raj, Jon, Al’a, Jenn, and others for being great coworkers. I would like to thank my committee members Dr. Loeb and Dr. Wang for helping guide me through my PhD over the past four and a half years. Additionally, I would like to thank both Dr. Northwood for agreeing to be my Outside Departmental reader and Dr. Baumgartner from the University of Calgary for taking the time to be my External Examiner. Over the past nine years, my parents have provided me with a tremendous amount of support. They have been the best Mother and Father that a Son could ask for. My wife, Olga, and my daughter Abby, have been my inspiration. They make every day worth living. Finally, I feel it is necessary to thank my undergraduate supervisor Dr. Ragonga. I had no clue as to what I wanted to accomplish in life until I had the pleasure of working for him. He showed me with dedication and hard work that anything is possible. ! vii! Table of Contents Declaration of Co-Authorship/Previous Publication ..................................................... iii Abstract .............................................................................................................................. iv Dedication ......................................................................................................................... vi Acknowledgements ......................................................................................................... viii List of Figures ..................................................................................................................... x List of Schemes ................................................................................................................. xv List of Tables ................................................................................................................... xvi List of Abbreviations ..................................................................................................... xvii Chapter 1 – Introduction ................................................................................................... 1 1.1 Pnictogens ......................................................................................................... 1 1.2 Lewis Structures ..............................................................................................
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