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Synthesis, Characterization, and Reactivity of Organometallic Complexes of Early and Late Metals and the Functionalization of Polydienes Bradley M

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Synthesis, Characterization, and Reactivity of Organometallic Complexes of Early and Late Metals and the Functionalization of Polydienes Bradley M Iowa State University Capstones, Theses and Graduate Theses and Dissertations Dissertations 2019 Synthesis, characterization, and reactivity of organometallic complexes of early and late metals and the functionalization of polydienes Bradley M. Schmidt Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/etd Part of the Inorganic Chemistry Commons Recommended Citation Schmidt, Bradley M., "Synthesis, characterization, and reactivity of organometallic complexes of early and late metals and the functionalization of polydienes" (2019). Graduate Theses and Dissertations. 17095. https://lib.dr.iastate.edu/etd/17095 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Graduate Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. Synthesis, characterization, and reactivity of organometallic complexes of early and late metals and the functionalization of polydienes by Bradley M. Schmidt A dissertation submitted to the graduate faculty in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Major: Inorganic Chemistry Program of Study Committee: Aaron D. Sadow, Major Professor Wenyu Huang Levi Stanley Javier Vela Theresa Windus The student author, whose presentation of the scholarship herein was approved by the program of study committee, is solely responsible for the content of this dissertation. The Graduate College will ensure this dissertation is globally accessible and will not permit alterations after a degree is conferred. Iowa State University Ames, Iowa 2019 Copyright © Bradley M. Schmidt, 2019. All rights reserved. ii To my late grandparents, Dan & Arjes Youngblade, without your support, encouragement, and devotion this would not have been possible. iii TABLE OF CONTENTS Page ACKNOWLEDGMENTS v ABSTRACT vii CHAPTER 1. INTRODUCTION General Introduction 1 Thesis Organization 5 References 7 CHAPTER 2. REDOX CHEMISTRY OF BIS(OXAZOLINYL)- CYCLOPENTADIENYL AND -FLUORENYL RHODIUM AND IRIDIUM ORGANOMETALLIC COMPOUNDS 10 Abstract 10 Introduction 11 Results and Discussion 14 Conclusion 41 Experimental 43 References 58 CHAPTER 3. ZWITTERIONIC TRIVALENT (ALKYL)LANTHANIDE COMPLEXES IN ZIEGLER-TYPE BUTADIENE POLYMERIZATION 63 Abstract 63 Introduction 64 Results and Discussion 67 Conclusion 97 Experimental 101 References 104 iv CHAPTER 4. ACTIVATION STUDIES OF Nd{C(SiHMe2)3}3 AND THEIR IMPACTS TOWARD DIENE POLYMERIZATION REACTIVITY AND SELECTIVITY 109 Abstract 109 Introduction 109 Results and Discussion 112 Conclusion 132 Experimental 134 References 135 CHAPTER 5. END GROUP FUNCTIONALIZATION AGENTS FOR POLYDIENE 139 Abstract 139 Introduction 140 Results and Discussion 142 Conclusion 173 Experimental 175 References 185 CHAPTER 6. CONCLUSION 188 General Conclusion 188 v ACKNOWLEDGMENTS I would like to start by thanking my advisor, Dr. Aaron D. Sadow, for his continued support throughout my graduate school journey. Curiosity and a passion for exploration of chemistry is something Dr. Sadow has instilled in me throughout my time at Iowa State and will be something I cherish and carry with me in my future career path. I would also like to thank my committee members, Dr. Igor Slowing, Dr. Levi Stanley, Dr. Javier Vela, and Dr. Theresa Windus, as well as my former committee member Dr. L. Keith Woo for their encouragement and support. In addition, I would also like to thank the department faculty, especially Dr. Sarah Cady, and department staff for encouraging me and at times criticizing my work in order for me to produce my best possible end results. My time at Iowa State University has molded me into an individual who will approach future challenges with an open mind and never be satisfied with the easy path but rather the path which generates the most accurate and reliable results. I would also like to thank past and present Sadow Group Members for their support and encouragement in not only the good but more importantly the challenging times. I would like to give a special mention to Mr. Patrick Dilsaver and Dr. Zak Weinstein for their friendship and mentorship in matters of science and life, while they may not know the extent of their impact, these are friendships that got me into and through graduate school. Kevin Basemann also deserves a special thank you for the role he played in multiple projects we worked on together and for his unwavering opinions on all matters, may they be correct or not, he ensured each day in lab was unique and worth experiencing. And finally, to the ladies of east-side office, Yang Yun, Kasuni, Smita (teammate for life), and former members Dr. Aradhana Das it was a pleasure opening vi your eyes to parts of American Culture there is no need for you to have learned, but I enjoyed sharing them regardless. To my family, I would like to express my gratitude, appreciation, and thanks to you all. You often expressed some level interest when I discussed the frustrations of “wet” solvents, “crystals” that don’t diffract, and a robot that misbehaves and/or breaks even if you truly had no idea what I was talking about. At some level, you all had a part in this journey and words alone cannot express my appreciation. To my parents, Dan & Chris, while at times we disagree on tactics, practices, and other parts of life neither of you have ever allowed that to hinder your support for me and the path I wander. You both, in your own ways, have provided me with every possible opportunity to succeed in life and will be forever grateful for that. To my brothers, you have provided valuable outlets for stress, life lessons (both dos and do nots), and have continued to remind me that my best asset in life has not been my brain but rather an unwavering heart that puts other first and myself second. To my Uncle Pat, I thank you for forever being a thirteen- year old boy with an adult pay check. Your encouragement for curiosity and knowledge have taken me to places and generated experiences which would have never been had without your gentle nudges. Finally, to the rest of my family (who will not be individually named) thanks for always asking “You aren’t done yet?” or “When will you finish?” it helped motivate me to stick with it and finish. Oh, and I guess you had some kind words to say as well; thank you for those. vii ABSTRACT A series of rhodium and iridium organometallic complexes supported by 1- Me2 cyclopentadienyl-1,1-bis(4,4-dimethyl-2-oxazolinyl)ethane (MeC(Ox )2(C5H4); M Me2 Bo Cp) and 1-fluorenyl-1,1-bis(4,4-dimethyl-2-oxazolinyl)ethane (MeC(Ox )2(C13H8); BoMFlu) are described. Metalation of BoMCp readily occurrs through salt metathesis from a thallium intermediate or protonolysis with appropriate metal precursors. In contrast, metalation of the more basic BoMFlu ligand requires in situ generation of a potassium carbanion by potassium benzyl and subsequent salt metathesis with appropriate metal precursors. The piano-stool complexes of BoMCpM (M = Rh or Ir) were unreactive to substitution chemistry and forcing condition required for C–H activation reactions resulted in decomposition of catalysts prior to successful reactions. However, the two- M M III electron oxidation of Bo CpRh(C2H4)2 with Br2 results in Bo CpRhBr2, a new Rh species. BoMFluM (M = Rh or Ir) complexes readily underwent substitution chemistry. In M addition, Bo FluRhL2 (L2 = C8H12 or C16H12) displayed unique electrochemistry of two reversible 1-electron oxidations were RhII species could be generated in solution. A series of lanthanide organometallic complexes, Ln{C(SiHMe2)3}3 (Ln = La, Ce, Pr, Nd) were activated by the abstraction of Si–H with 1 and 2 equivalents B(C6F5)3 to generate Ln{C(SiHMe2)3}2HB(C6F5)3 and Ln{C(SiHMe2)3{HB(C6F5)3}2 respectively. The addition of AlR3 (R = Me or iBu) to Ln{C(SiHMe2)3}3 resulted in the complexation of the weaker lewis acid rather than Si–H abstraction. The mono- and di-alkyl complexes, with AliBu3 co-catalysts, are active in butadiene polymerization. Neodymium and cerium show the highest activity and all lanthanides showed a ~50:50 selectivity for cis- 1,4:trans-1,4 insertions, with exception of lanthanum which showed a slightly higher viii selectivity for trans-1,4. Further studies with precatalysts Nd{C(SiHMe2)3}3 indicate a polymerization with living character with respect to reaction time but also showed a dependence of molecular weight on Nd:AliBu3 ratio supporting the proposed chain- transfer mechanism. Polymerization in saturated hydrocarbon solvent (heptane) improved cis-1,4 selectivity to nearly 90% with Nd{C(SiHMe2)3}3 pre-catalyst. Nd{C(SiHMe2)3{HB(C6F5)3}2 with 10 equivalents AliBu3 was >95% selective in the polymerization of isoprene to cis-1,4 polyisoprene with good activity in toluene. In contrast, Nd{C(SiHMe2)3}2HB(C6F5)3 was less active in the polymerization of isoprene and displayed a lower selectivity yielding ~40% trans-1,4 polyisoprene. The activation of Nd{C(SiHMe2)3}3 in toluene with different protocols containing the organochloride Ph3CCl were also successful for cis-1,4 selective polymerizations of isoprene with narrow polydispersity. In addition, activation protocols with Ph3CCl improved the cis-1,4 selectivity of polybutadiene to 90% and above but with more broad polydispersity. Functionalizing agents for the functionalization of polydienes were synthesized from modified literature procedures. The modifications allowed for higher yields for compounds such as (EtO)3Si-CºC-Si(OEt)3. The application of (EtO)3Si-CºC-Si(OEt)3 as a quenching agent for neodymium-based diene polymerizations resulted in the incorporation of silyl functionalized polydiene and improved physical properties of the resulting rubber composites.
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