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Heavy P-Block Analogues of Dithiazolyl Radicals

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Heavy P-Block Analogues of Dithiazolyl Radicals University of Windsor Scholarship at UWindsor Electronic Theses and Dissertations Theses, Dissertations, and Major Papers 12-17-2015 Heavy p-Block Analogues of Dithiazolyl Radicals Thao Thi Phuong Tran University of Windsor Follow this and additional works at: https://scholar.uwindsor.ca/etd Recommended Citation Tran, Thao Thi Phuong, "Heavy p-Block Analogues of Dithiazolyl Radicals" (2015). Electronic Theses and Dissertations. 5672. https://scholar.uwindsor.ca/etd/5672 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. HEAVY p-BLOCK ANALOGUES OF DITHIAZOLYL RADICALS By THAO THI PHUONG TRAN A Dissertation Submitted to the Faculty of Graduate Studies through the Department of Chemistry & Biochemistry in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy at the University of Windsor Windsor, Ontario, Canada 2015 © 2015 Thao Thi Phuong Tran Heavy p-Block Analogues of Dithiazolyl Radicals by Thao Tran APPROVED BY: __________________________________________________ P. Ragogna, External Examiner Western University __________________________________________________ D. Northwood Mechanical, Automotive & Materials Engineering __________________________________________________ C. Macdonald Department of Chemistry & Biochemistry __________________________________________________ S. Loeb Department of Chemistry & Biochemistry __________________________________________________ J. Rawson, Advisor Department of Chemistry & Biochemistry December 14, 2015 DECLARATION OF ORIGINALITY I hereby certify that I am the sole author of this thesis and that no part of this thesis has been published or submitted for publication except where indicated otherwise in this thesis. I certify 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 and have included copies of such copyright clearances to my appendix. 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 This thesis commences with an introduction to the chemistry and materials properties of dithiazolyl radicals and a review of previous research on the isolobal heterocyclic phosphorus-containing derivatives, particularly dithiaphospholes and diazaphospholes. P-chloro-1,3,2-benzo-dithiaphospholes were prepared from the condensation of - PCl 3 and 1,2-benzodithiols in good yield. Reduction afforded 2c,2 e P-P σ-bonded dimers containing a formal P II oxidation state which were characterised by X-ray diffraction. Re-oxidation generates the crystallographically characterised P- halogeno-1,3,2-benzo-dithiaphospholes. The synthesis and structural characterisation of the isolobal P-chloro-1,3,2-benzodiazaphospholes, C6H4(NR) 2PCl (R = H, Me, Et, COMe, COOMe) is described. The outcome of attempted reductive coupling was found to be sensitive to reaction conditions, affording the PII dimer alongside other decomposition products characterised by X- ray diffraction. Functionalisation of the P-chloro group by salt metathesis and/or condensation was used to prepare a series of poly-cyclic structures containing two or more diazaphosphole, dithiaphosphole and dithia-arsole rings linked via bridging units which were characterised by X-ray diffraction. The paddle-wheel molecules N(C 7H6S2Pn) 3 (Pn = P, As) were prepared by a stepwise condensation of Li[N(SiMe 3)2] with P-chloro-dithiaphosphole and As -chloro-dithia-arsole whereas the bis-triamide C 6H4(NR[C 6H4(NR) 2P]) 2 was prepared from condensation of the P-chloro-diazaphosphole with ortho -C6H4(NHR) 2. Treatment of P-chloro-dithiaphospholes or P-chloro-benzodiazaphospholes with MCl 3 (M = Al, Ga) generated a series of two-coordinate phosphenium cations whose structures were determined by X-ray crystallography. This methodology was extended to prepare the heavier dithia-arsenium and dithia-stibenium cations and the structure of the first benzodithia-arsenium cation is reported. These cations iv are Lewis acidic and form a series of 1:1 complexes with Ph 3E (E= P, As, Sb) which are characterised by multinuclear NMR. The dithiaphosphenium cation (as - its GaCl 4 salt) also forms adducts with dioxane and propylene oxide but is an efficient catalyst for the cationic ring opening polymerisation (CROP) of THF to form poly(THF), [O(CH 2)4]n. The conversion rate and yield is sensitive to reaction - conditions. Notably the corresponding AlCl 4 salt did not polymerise THF due to reformation of the P-chloro-dithiaphosphole and formation of the adduct, AlCl 3·2THF. The related arsenium and stibenium cations show limited activity as reagents for the CROP of THF. v DEDICATION I dedicate my dissertation to my Mom, my Dad, and my Family who have been loving me unconditionally, and guiding me to live a more fulfilling and more meaningful life. vi ACKNOWLEDGEMENTS First of all, I would like to express my highest gratitude to Professor Jeremy Rawson for granting me the opportunity to work in his group. I sincerely appreciate his guidance, help, support, patience, and friendship through my years of graduate study. I am grateful for his training in EPR spectroscopy (even if my samples were invariably silent!), single crystal X-ray diffraction, X-ray structure solution and refinement as well as computational chemistry. His assistance in collecting single crystal X-ray data, and completing structure solution and refinement is highly acknowledged. I also appreciate his great help in revising my thesis. I am especially thankful for his open-minded working styles in giving me total freedom environment to explore the phosphorus chemistry. Without his talent and encouragement, I could hardly approach and comprehend these new research areas. I am indebted to the current and previous members of the Rawson group. Dr. John Hayward and Dr. Muhammad Usman Anwar worked tirelessly to take care of the labs so that I have a clean and joyful workplace. Dr. Anwar is also acknowledged for showing me how to use the diffractometer, for helping me collect some single crystal X-ray data and do some preliminary structure solution. I would like to thank Adam Dunmore (Outstanding Scholar and 410 student) for his collaborative work and contributions to Chapter 3. Other group members are acknowledged for their help and making graduate studies a great and memorable time. I am grateful to my current and past committee members Professor Holger Eichhorn, Professor Ricardo Aroca, Professor Charles Macdonald, Professor Stephen Loeb, and Professor Derek Northwood, who have given me continuous support, help, and valuable feedback. I would like to thank the Natural Sciences and Engineering Research Council of Canada, University of Windsor, the Department of Chemistry & Biochemistry for the support in funding, administration, and maintenances of chemistry instruments. vii I would like to show appreciation towards Dr. Zhuo Wang for training me in air- sensitive techniques in my chemistry, Dr. Matthew Revington for his training on NMR spectrometer, Dr. Janeen Auld for undertaking mass spectroscopy and elemental analysis for some samples, Mr. Tuan Hoang for collecting powder X-ray data, Ms. Elizabeth Kickham and Ms. Marlene Bezaire for preparing the paperwork, and Mr. Al Ditchburn for repairing broken glassware. Most importantly, I would like to express greatest gratitude to my parents and my family for their continuous support, their care, their love, and their encouragement, and providing me with the meaning and purpose of life. viii TABLE OF CONTENTS DECLARATION OF ORIGINALITY ................................................................... iii ABSTRACT ............................................................................................................. iv DEDICATION ......................................................................................................... vi ACKNOWLEDGEMENTS ....................................................................................vii LIST OF TABLES .................................................................................................. xv LIST OF FIGURES ...........................................................................................
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