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University of Windsor Scholarship at UWindsor Electronic Theses and Dissertations Theses, Dissertations, and Major Papers 2005 Vanadium phosphinimide complexes for ethylene polymerization and the chemistry of phosphinimines and phosphine oxides with borane reagents Sarah Bess Hawkeswood University of Windsor Follow this and additional works at: https://scholar.uwindsor.ca/etd Recommended Citation Hawkeswood, Sarah Bess, "Vanadium phosphinimide complexes for ethylene polymerization and the chemistry of phosphinimines and phosphine oxides with borane reagents" (2005). Electronic Theses and Dissertations. 4500. https://scholar.uwindsor.ca/etd/4500 This online database contains the full-text of PhD dissertations and Masters’ theses of University of Windsor students from 1954 forward. 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The quality of this reproduction is dependent upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleedthrough, substandard margins, and improper alignment can adversely affect reproduction. In the unlikely event that the author did not send UMI a complete manuscript and there are missing pages, these will be noted. Also, if unauthorized copyright material had to be removed, a note will indicate the deletion. Oversize materials (e.g., maps, drawings, charts) are reproduced by sectioning the original, beginning at the upper left-hand corner and continuing from left to right in equal sections with small overlaps. ProQuest Information and Learning 300 North Zeeb Road, Ann Arbor, Ml 48106-1346 USA 800-521-0600 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Vanadium Phosphinimide Complexes for Ethylene Polymerization and The Chemistry of Phosphinimines and Phosphine Oxides with Borane Reagents By Sarah Bess Hawkeswood A Dissertation Submitted to the Faculty of Graduate Studies and Research 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 2005 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Library and Bibliotheque et 1 * 1 Archives Canada Archives Canada 0-494-09706-X Published Heritage Direction du Branch Patrimoine de Edition 395 Wellington Street 395, rue Wellington Ottawa ON K1A 0N4 Ottawa ON K1A 0N4 Canada Canada Your file Voire reference ISBN: Our file Notre reference ISBN: NOTICE: . AVIS: The author has granted a nom L'auteur a accorde une licence non. exclusive exclusive license allowing Library permettant a la Bibliotheque et Archives and Archives Canada to reproduce, Canada de reproduire, publier, archiver, . publish, archive, preserve, conserve, sauvegarder, conserver, transmettre au public communicate to the public by par telecommunication ou par I'lnternet, preter, telecommunication.or on the Internet, distribuer et vendre des theses partout dans loan, distribute and sell theses le monde, a des fins commerciales ou autres, worldwide, for commercial or non­ sur support microforme, papier, electronique commercial purposes, in microform, et/ou autres formats. paper, electronic and/or any other formats. The author retains copyright L'auteur conserve la propriete du droit d'auteur ownership and moral rights in et des droits moraux qui protege cette these. this thesis. Neither the thesis Ni la these ni des extraits substantiels de nor substantial extracts from it celle-ci ne doivent etre imprimes ou autrement may be printed or otherwise reproduits sans son autorisation. reproduced without the author's permission. In compliance with the Canadian Conformement a la loi canadienne Privacy Act some supporting sur la protection de la vie privee, forms may have been removed quelques formulaires secondaires from this thesis. ont ete enleves de cette these. While these forms may be included Bien que ces formulaires in the document page count, aient inclus dans la pagination, their removal does not represent il n'y aura aucun contenu manquant. any loss of content from the thesis. Canada Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. IOZT72C © 2005 Sarah Bess Hawkeswood Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Abstract A reproducible and high yielding synthesis of the vanadium imide phosphinimide complexes of the general formula V(NAr)(NPR. 3)Cl2 (Ar = Ph, C6H3-2 ,6 -/-Pr2; R = /-Pr, t- Bu, Ph) has been developed. These complexes upon activation by methylaluminoxane demonstrated low to moderate ethylene polymerization activities comparable to published vanadium imide complexes. The dichloride derivatives react readily with a variety of alkali metal salts and Grignard reagents to produce vanadium imide phosphinimide thiolate, alkyl, aryl, amide and alkoxide complexes. In the presence of Zn, reduction of V(NPh)(NP/-Bu 3)Cl2 occurred to afford what is proposed to be a vanadium(IV) imide bridged dimeric species (V(p-NPh)(NP/-Bu 3)Cl)2. The reaction of pinacolborane with phosphinimines (HNPR 3) proceeds via two observable reaction pathways: a metathesis reaction, in which hydrogen gas is evolved, or the reduction of phosphorus, in which the corresponding borylamine and tertiary phosphine are formed. Experimental results and a DFT study showed that the preferred mechanism is dictated by the steric bulk of the R groups. The analogous reductions of phosphine oxides with pinacolborane gave tertiary phosphines and 0 (Bpin) 2. Alternative synthetic procedures and subsequent reactions of 0 (Bpin )2 with both metal and main group complexes were investigated. These reactions led to the synthesis of Zr(C5H5)2(OBpin) 2, [/-Bu3PNH2][pinB(OBpin) 2], and degradation products. iV-borylphosphinimines of the general formula (R 3Pp-NBcat)x (cat = O2C6H4; R = Et, n-Bu, /-Pr, Ph, t-Bu; R3 = h-Bu(/-Bu)2; x = 1,2) were synthesized. The dimeric or monomeric nature of the above compounds were probed by X-ray and NMR methods, revealing that the steric bulk of the R groups affected the preferred bonding mode of the complexes in solution and in solid state. Therefore, metathesis reactions have led to the synthesis of both vanadium phosphinimide complexes and A-borylphosphinimine complexes. It has been determined that the steric bulk of the substituents of the phosphinimine affect the bonding mode of the vV-borylphosphinimine complexes and their reactivity with boranes. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. V Dedication This work is dedicated to my family, for your unwavering love, encouragement and support that continued to fill me up on this rollercoaster ride called graduate school. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Acknowledgements There are numerous folks I need to acknowledge with thanks for their help and support in completing this work. I would like to thank the Stephan group members both past and present for creating a work environment that was welcoming and productive, especially: Dr. Chad Beddie, Ms. Lourisa Cabrera, Mr. Steve Clemens, Dr. Silke Courtenay, Dr. Todd Graham, Ms. Sharonna Greenberg, Dr. Emily Hollink, Dr. Aaron Hoskin, Ms. Rodica Leu, Mr. Jason Masuda, Ms. Jenny McCahill, Ms. Edyta Urbanska, Dr. Denise Walsh and Ms. Nancy Yue. I would like to thank Dr. Emily Hollink for constantly helping me in the lab and for being my kindred spirit through grad school. I would like to thank Dr. Aaron Hoskin for watching out for me and encouraging me to stick with this. I would like to thank Mr. Jason Masuda for patiently helping me with the X-ray diffractometer and in the lab. I would like to thank Dr. James Gauld and Dr. Chad Beddie for their advice with the computational study in this thesis. I would like to thank Mr. Mike Fuerth for all of his help with the NMR spectrometers and listening to me chatter on in the NMR room. I would like to acknowledge NOVA Chemicals Corporation for performing the GPC analyses of the polyethylene generated from the work in Chapter 2. I would like to thank Dr. Emily Hollink, Mr. Jason Masuda, Ms. Sharonna Greenberg and Dr. James Gauld for their help in editing this thesis. Thank you. I would like to thank my husband for loving me, marrying me, listening to me and making me smile everyday. I would like to thank my mom for being

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