University of Windsor Scholarship at UWindsor Electronic Theses and Dissertations Theses, Dissertations, and Major Papers 1-1-2019 Synthesis, Characterization, and Reactivity of Chelating Ligand Complexes of Group 13-15 Elements Ala'aeddeen Swidan University of Windsor Follow this and additional works at: https://scholar.uwindsor.ca/etd Part of the Chemistry Commons Recommended Citation Swidan, Ala'aeddeen, "Synthesis, Characterization, and Reactivity of Chelating Ligand Complexes of Group 13-15 Elements" (2019). Electronic Theses and Dissertations. 7761. https://scholar.uwindsor.ca/etd/7761 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). 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Synthesis, Characterization, and Reactivity of Chelating Ligand Complexes of Group 13-15 Elements By Ala’aeddeen Swidan A Dissertation Submitted to the Faculty of Graduate Studies through the Department of Chemistry and Biochemistry in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy at the University of Windsor Windsor, Ontario, Canada 2019 © 2019 Ala’aeddeen Swidan Synthesis, Characterization, and Reactivity of Chelating Ligand Complexes of Group 13-15 Elements by Ala’aeddeen Swidan APPROVED BY: ______________________________________________ D. Richeson, External Examiner University of Ottawa ______________________________________________ J. Gagnon Earth and Environmental Sciences ______________________________________________ J.R. Green Department of Chemistry and Biochemistry ______________________________________________ S. Johnson Department of Chemistry and Biochemistry ______________________________________________ C. Macdonald, Advisor Department of Chemistry and Biochemistry June 17, 2019 DECLARATION OF CO-AUTHORSHIP AND PREVIOUS PUBLICATION Co-Authorship I hereby declare that this dissertation incorporates material that is a result of joint research, as follows: Chapter 2 of the dissertation contains results published in the original research communication “2,6-Bis(benzimidazol-2-yl)pyridines as more electron-rich and sterically accessible alternatives to 2,6-bis(imino)pyridine for group 13 coordination chemistry” (Swidan, A.; Binder, J. F.; St. Onge, P. B.; Suter, R.; Burford, N.; Macdonald, C. Dalton Trans. 2019, 1284–1291). Mr. St. Onge contributed to the synthesis and characterization of some of the reported compounds, Mr. Binder contributed to the computational studies, Dr. Macdonald and Dr. Suter helped in the writing and editing of the manuscript. Chapter 3 of the dissertation contains results published in the original research article “2,6-Bis(benzimidazol-2-yl)pyridine Complexes of Group 14 Elements” (Swidan, A.; St. Onge, P. B.; Binder, J. F.; Suter, R.; Burford, N.; Macdonald, C. Dalton Trans. 2019, 48, 7835-7843). Mr. St. Onge contributed to the synthesis and characterization of some the reported compounds, Mr. Binder contributed to the computational studies, Dr. Macdonald helped in the writing, editing and provided ideas to investigate and include in the manuscript. Chapter 5 of the dissertation contains results published in the original research article “Tris(benzoimidazol)amine (L) complexes of pnictogen(III) and pnictogen(V) cations and assessment of the [LP]3+/[LPF2]3+ redox couple” (Swidan, A.; Suter, R.; Macdonald, C. L. B.; Burford, N. 2018, 5837–5841). Dr. Suter contributed to the synthesis and characterization of some of the reported compounds as well as in the computational studies, writing, and editing of the manuscript. Dr. Macdonald contributed to the computational studies, writing, and editing of the manuscript. III DECLARATION OF CO-AUTHORSHIP AND PREVIOUS PUBLICATION 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 dissertation and have obtained written permission from each of the co-author(s) to include the above material(s) in my dissertation. I certify that, with the above qualification, this dissertation, and the research to which it refers, is the product of my own work. Previous Publication This dissertation includes 3 original papers that have been previously published/submitted for publication in peer-reviewed journals, as follows: Dissertation Publication title/full citation Publication Chapter status Chapter 2 “2,6-Bis(benzimidazol-2-yl)pyridines as more electron-rich and Published sterically accessible alternatives to 2,6-bis(imino)pyridine for group 13 coordination chemistry” Swidan, A.; Binder, J. F.; St. Onge, P. B.; Suter, R.; Burford, N.; Macdonald, C. Dalton Trans. 2019, 1284–1291. Chapter 3 “2,6-Bis(benzimidazol-2-yl)pyridine Complexes of Group 14 Published Elements” Swidan, A.; St. Onge, P. B.; Binder, J. F.; Suter, R.; Burford, N.; Macdonald, C. Dalton Trans. 2019, 48, 7835-7843. Chapter 5 “Tris(benzoimidazol)amine (L) complexes of pnictogen(III) and Published pnictogen(V) cations and assessment of the [LP]3+/[LPF2]3+ redox couple” Swidan, A.; Suter, R.; Macdonald, C. L. B.; Burford, N. 2018, 5837–5841. I certify that I have obtained written permission from the copyright owner(s) to include the above published material(s) in my dissertation. I certify that the above material describes work completed during my registration as a graduate student at the University of Windsor. General I declare that, to the best of my knowledge, my dissertation 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 IV DECLARATION OF CO-AUTHORSHIP AND PREVIOUS PUBLICATION in my dissertation, 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 written permission from the copyright owner(s) to include such material(s) in my dissertation. I declare that this is a true copy of my dissertation, including any final revisions, as approved by my dissertation committee and the Graduate Studies office and that this dissertation has not been submitted for a higher degree to any other University or Institution. V ABSTRACT 2,6-bis(benzimidazol-2-yl)pyridine derivative (G-BZIMPY, G = NBn, N(3,5- CF3)Bn, N-allyl and O) have been used as pincer ligands to coordinate and isolate various group 13-15 complexes. For Group 13, treatment of G-BZIMPY with two equivalents of GaCl3 results in the self-ionization products [G-BZIMPYGaCl2][GaCl4]. This Ga(III) complex can be reduced to a Ga(I) centre using K2[Fe(CO)4] as a reducing agent to result in the Ga(I) complex [(NBn-BZIMPY)(Cl)Ga–Fe(CO)4] (Chapter 2). Group 14 complexes of G-BZIMPY have been synthesized in a similar fashion through the self-ionization reactions of G-BZIMPY with two equivalents of MCl2 (M = Ge, Sn) to yield [G-BZIMPYMCl][MCl3]. Attempts to reduce these complexes into the M(0) centre were not successful. Other reactivities and UV-vis studies are detailed in this dissertation (Chapter 3). Comparison of group 13 and 14 complexes of G-BZIMPY to complexes of the structurally similar bis(imino)pyridine (DIMPY) are studied and reveal G-BZIMPY as a stronger donor than DIMPY for group 13 coordination. For group 15 elements, treatment of PnCl3 (Pn = P, As, Sb) with G-BZIMPY does not yield any reactivity, however, the addition of TMS-OTf (Trimethylsilyl trifluoromethanesulfonate) results in the isolation of [G-BZIMPYPnCl][OTf]2 (Chapter 4). In-addition, a tetradentate ligand tris((1-ethyl-benzoimidazol-2- yl)methyl)amine (BIMEt3) has been investigated. A series of cationic complexes involving a pnictogen(III) (Pn = P, As, Sb) centre coordinated to BIMEt3 have been synthesized and comprehensively characterized. Oxidation of [P(BIMEt3)]3+ with VI ABSTRACT XeF2 provides access to [PF2(BIMEt3)]3+ representing the first structurally characterized example of a phosphorus(V) centred trication (Chapter 5). Attempts to synthesize an anionic carbon(0) are detailed in chapter 6. Although obtaining an anionic carbon(0) was not successful, it lead to a series of interesting compounds and results. Compounds containing carbon centre behave differently than their heavier group-14 analogues of the same bidentate anionic bisphosphine ligand. VII DEDICATION To Family and Science! VIII ACKNOWLEDGEMENTS My academic journey would not have been possible if it wasn’t for the support of my community. My community has provided me with the necessary environment and tools to be successful and for that, I am eternally gratefully and will always be indebted to this loving and caring community. My supervisor, Dr. Charles L. B. Macdonald, has been very supportive throughout