University of Windsor Scholarship at UWindsor Electronic Theses and Dissertations Theses, Dissertations, and Major Papers 4-30-2018 New Polyether Complexes of Germanium(II) and Tin(II): Synthesis, Structural Characterization and Reactivity Alina Maria Secara University of Windsor Follow this and additional works at: https://scholar.uwindsor.ca/etd Recommended Citation Secara, Alina Maria, "New Polyether Complexes of Germanium(II) and Tin(II): Synthesis, Structural Characterization and Reactivity" (2018). Electronic Theses and Dissertations. 7449. https://scholar.uwindsor.ca/etd/7449 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. New Polyether Complexes of Germanium(II) and Tin(II): Synthesis, Structural Characterization and Reactivity By Alina Maria Secara A Thesis Submitted to the Faculty of Graduate Studies through the Department of Chemistry and Biochemistry in Partial Fulfillment of the Requirements for the Degree of Master of Science at the University of Windsor Windsor, Ontario, Canada 2018 © 2018 Alina M. Secara New Polyether Complexes of Germanium(II) and Tin(II): Synthesis, Structural Characterization and Reactivity by Alina Maria Secara APPROVED BY: ______________________________________________ J. Gagnon Department of Earth and Environmental Sciences ______________________________________________ S. Loeb Department of Chemistry and Biochemistry ______________________________________________ C. Macdonald, Advisor Department of Chemistry and Biochemistry April 26, 2018 Declaration of Co-Authorship/Previous Publication I. Co-Authorship I hereby declare that this thesis incorporates material that is result of joint research, as follows: Chapter 2 and 3 contain results included in the manuscript accepted for publication entitled “Synthesis and Structural Characterization of New Polyether Complexes of Germanium(II) and Tin(II)” (Alina M. Secara, Justin F. Binder, Ala’aeddeen Swidan and Charles L.B. Macdonald, Canadian Journal of Chemistry, 2018 ). I and Justin F. Binder prepared the manuscript. Justin F. Binder performed the X-ray crystallography experiments. I synthesized and further characterized all the complexes in this work. Ala’aeddeen Swidan performed the X-ray crystallography experiment for the water adduct (H2O·SnOTf(dibenzo[24]crown-8)][OTf]) presented in chapter 3 and the elemental analysis. My supervisor, Dr. Charles L.B. Macdonald refined and solved the crystal structures and provided significant edits to the manuscript. Chapter 4 contains the preliminary results of the investigation into reactivity of the new polyether complexes. I synthesized and characterized all the compounds in this work. Ala’aeddeen Swidan performed the elemental analysis for one of the compounds (C 26 H32 F6Sn 2O14 S2) in this work. The results presented in this chapter are unpublished. 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 iii 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. Previous Publication This thesis includes 1 original papers that have been previously published/submitted for publication in peer reviewed journals, as follows: Thesis Chapter Publication title/full citation Publication status Chapter 2 “Synthesis and Structural Characterization of Accepted New Polyether Complexes of Germanium(II) and Tin(II)”, Alina M. Secara , Justin F. Binder, Ala’aeddeen Swidan and Charles L.B. Macdonald, Canadian Journal of Chemistry, 2018 Chapter 3 “Synthesis and Structural Characterization of Accepted New Polyether Complexes of Germanium(II) and Tin(II)”, Alina M. Secara , Justin F. Binder, Ala’aeddeen Swidan and Charles L.B. Macdonald, Canadian Journal of Chemistry, 2018 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 a graduate student at the University of Windsor. iv III. General 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. v Abstract The chemistry involving group 14 cations and polyether ligands has been an area of great interest in the last decade. The Macdonald Group has long been interested in the synthesis, characterization and reactivity of polyether complexes containing group 13 and 14 elements in low oxidation state. Recently, our group has demonstrated that the properties of crown ethers and of the more flexible glyme ligands make them ideal for the stabilization of group 14 elements in the +2 oxidation state. Many of the resulting polyether complexes hold great potential for further reactivity in that they may act as Lewis acids to simple nucleophiles like water and ammonia while retaining a non-bonding electron pair. A series of complexes of crown ethers and glymes with Ge(II) and Sn(II) bromide have been synthesized. Specifically, [GeBr([15]crown-5)][GeBr 3], [GeBr([18]crown-6)][GeBr 3], [GeBr(triglyme)][GeBr 3], [GeBr(tetraglyme)][GeBr 3], [SnBr([18]crown-6)][SnBr 3], [Sn([15]crown-5) 2][SnBr 3]2, [SnBr(triglyme)][SnBr 3] and [SnBr(tetraglyme)][SnBr 3] have been fully characterized including by single crystal X-ray diffraction. [GeBr(triglyme)][GeBr 3] and [GeBr(tetraglyme)][GeBr 3] represent the first examples of crystallographically confirmed glyme complexes of germanium. The synthesis of [GeBr(dibenzo[24]crown-8)][GeBr 3] and [GeCl(dibenzo[24]crown-8)][GeCl 3] are also reported, along with the crystal structure of the latter’s water adduct, which features the water molecule adjacent to the GeCl + ion within the cavity of the crown ether. Recrystallization of the salt [SnOTf(dibenzo[24]crown-8)][OTf] generated crystals of the water complex suitable for examination by single crystal X-ray diffraction. vi Dedication Dedicated to my loving husband Tudor and my wonderful daughters, Teodora and Alexandra! vii Acknowledgements Since my graduation from university, my life has changed and become drastically different. Immigrating to Canada was one of the most significant events of my life; however, while my life in a new country progressed very quickly, one of my biggest dreams of continuing my education seemed to progressively fade as the years passed by. Because of this, I would like to express my sincere gratitude to Dr. Chuck Macdonald, my supervisor. I am very grateful to him for this special opportunity, as it has allowed me to reconnect and continue pursuing my aspirations, as well as obtaining my masters. I would like to thank Chuck especially for his patience, encouragement and guidance, and for all the advice he has given me – including the mini chemistry lessons when a question arose. Thank you very much for everything! I would like to thank Dr. Steve Loeb and Dr. Joel Gagnon for agreeing to be on my examination committee and for taking the time to read my thesis. I would like to thank all the Macdonald group members, past and present. Special and sincere thanks go to Justin for his continued support regarding my research work and especially for my first crystal structure, AMS 22. Also, special thanks go to Ala for always being a great help. I would like to thank Steph for helping me get started in the lab and for all the help during these two years. Thank you to Fawzia for being a good colleague and for all the talks we had, also to Emily, Max, Brad and Lara. I would also like to thank Zeinab and Mitch from the Rawson group for their helpful advice. viii Extended thanks go to Dr. Matt Revington for his help and guidance with NMR spectroscopy and Dr. Janeen Auld for EA. Thank you to Marlene for always keeping us on track and to Beth for all the nice conversations we had. Thank you to Nedhal for her encouragement. I would also like to thank the great professors that I have had, especially Dr. Steve Loeb, Dr. Jeremy Rawson and Dr. Tricia Charmichael for their awesome work. Especially, to Dr. Loeb for his patience and for listening to my first presentation, probably one of the longest presentations in his class. Most importantly, I wish to thank my loving and supportive husband, Tudor and my two wonderful daughters, Teodora and Alexandra for their unending love, understanding and encouragement. Especially to you Tudor, I would not have accomplished any of this without you! ix Table of Contents Declaration of Co-Authorship/Previous Publication ...................................................