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AND MID-VALENT ORGANOMETALLIC URANIUM CHEMISTRY by Caleb J

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AND MID-VALENT ORGANOMETALLIC URANIUM CHEMISTRY by Caleb J EXPANSION OF LOW- AND MID-VALENT ORGANOMETALLIC URANIUM CHEMISTRY by Caleb J. Tatebe A Dissertation Submitted to the Faculty of Purdue University In Partial Fulfillment of the Requirements for the degree of Doctor of Philosophy Department of Chemistry West Lafayette, Indiana August 2019 2 THE PURDUE UNIVERSITY GRADUATE SCHOOL STATEMENT OF COMMITTEE APPROVAL Dr. Suzanne C. Bart, Chair Department of Chemistry Dr. Corey M. Thompson Department of Chemistry Dr. Christopher Uyeda Department of Chemistry Dr. David R. McMillin Department of Chemistry Approved by: Dr. Christine A. Hrycyna Head of the Graduate Program 3 Soli Deo Gloria 4 ACKNOWLEDGMENTS I would be where am I today without the enduring support from my wife, Vanessa. From the willingness to move out to Indiana with me, to dealing with the late nights without me being home – there is nothing that Vanessa wouldn’t do for me and I am grateful to spend my life with her. If, for some reason, anyone is reading this, bear with me. There is a story to tell about how I made it through graduate school. I suppose it really began with the seeds sown by my high school chemistry teacher, Amy Hays. I was fortunate enough to attend Warren Gamaliel Harding High School when it still housed a full diploma for the International Baccalaureate (IB) program. For this program, I did three years of chemistry in high school; at the time, I just thought chemistry was much cooler than biology and I needed a higher- level science! My first research experience was at Youngstown State University (YSU) while in Dr. Tim Wagner’s 1516L course which exposed undergraduate students to real-life research as part of the course. For me, this meant preparing series of perovskites (AMX3) with mixed ratios at the A or M site, as well as their analysis. I was hooked immediately, and with the guidance of Ashley Wolf, I was able to help future groups of students in this project, as well. Getting to help mentor students made me realize that I really loved helping others in the discovery process, which is where I first thought about teaching and mentoring more seriously. As I continued to mentor students over the next two and a half years, I began doing research in an organic synthetic group with Dr. Peter Norris. Working in the Norris lab gave me an immense appreciation for organic synthesis and methodology, but I knew that my heart was not in “traditional” organic synthesis as most groups were selling their chemistry in 2014. I would have never imagined that I would have been able to return to YSU and work in a professional capacity and as I write this, I am looking forward to this journey with great anticipation. I would have never applied to Purdue’s graduate program without the suggestion from my old labmate and lifetime friend Kyei Baffour. Kwaku convinced me that Purdue would be a good program for both of us and the rest is history. I wish Kyei all the best as he heads to Vanderbilt for his post-doc this summer! 5 There are many people within Purdue’s chemistry department that are integral to my success as a graduate student. One thing that unifies all of these people is that they all put themselves aside to ensure that you can transition into the program, acclimate to a group, research efficiently, and ultimately succeed. It starts when you are accepted into the program and you get your first e-mail from Betty Hatfield. I’m not sure how many people really understand what a massive undertaking a symposium weekend can be, but I think that’s because Betty does an outstanding job of organizing this large event. Once you arrive to campus, you would be wise to get acquainted with Rob Reason. On a daily basis, Rob will do whatever it takes to make sure that your time at Purdue is as stress-free as he can make it. Jeanne Meyer is also of note on this list. I came to this department at a time when Kurt was on his way out [we overlapped for one year] and Jeanne was changing to his coordinator position. I enjoyed the better part of three years working closely with Jeanne when I was a head TA for 25X. Being new to our job titles at the same time always galvanized us and projected us to working to better the undergraduate teaching labs. In this vein, I want to acknowledge Stefan Paula. In addition to Jeanne and myself, Stefan was also in a new role at Purdue and we tackled supervising these lab sections together. I really appreciated how Stefan immediately had the perfect balance of being relaxed and professional in his approach to handling the lab sections. It is something that I hope to emulate in my further endeavors! [Congratulations and best wishes to Stefan at UC-Sacramento, by the way] My time at Purdue was also made easier by the procurement and business offices within the department. It was overwhelming for me when I first learned of how vast the business office is for Purdue chemistry. It didn’t take long for me to learn about how vital these persons were to my time as a graduate student. Specifically, Jane Johanning was my point- person for expense, group purchases, and payroll concerns. Jane was always able to make time to answer my questions whenever I had them. It wasn’t much longer until I was ordering my own consumables and chemicals for myself or the group. As one might expect, this gets you acquainted with Darci Decamp and Suzy Gustafson – Darci and Suzy are two of the most helpful and honest people I met within the department and were no doubt crucial to my successes. 6 Some additional luxuries of being at a large department are the amenities in instrumentation and support staff. From the Amy Facility’s Research Instrumentation Center (Pat Bishop), to PINMRF (John Harwood, Jerry Hirschinger), and to the X-ray laboratory (Phil Fanwick, Matt Zeller). Special mention to Matt Zeller, who came with me from YSU to Purdue to fill the role of crystallographer shortly after I started at Purdue. I would like to also acknowledge all of my committee members for their support throughout the years. In addition to Professors David McMillin, Corey Thompson, and Chris Uyeda, I made a number of great friends and colleagues along the way. I would have to name those which have made significant contributions to my graduate school experience at Purdue; including, but not limited to Dr. John Kiernicki, Dr. Kwaku Kyei-Baffour, Dr. Ian Powers, Adharsh Raghavan, Dr. Talia Steiman, Jake Werth. On a chemistry note, I am extremely grateful for the pioneering work that the late Jerry Trofimenko has contributed to my own career. Scorpionate ligands have richly enhanced the field of coordination chemistry and catalytic processes. A special mention to the fellow f-block chemists and for the ground work that they laid for f-element complexes which employ scorpionate ligands. The lion’s share of this work was reported by Isabel Santos, Keith Bagnall, and Josef Takats – I could not imagine life without Tp*2UI! I certainly could not achieve all of the chemistry and much more without the guidance and mentorship provided by Suzanne. Throughout my five years at Purdue, I was able to focus and harness the mental framework for how I would mentor students and function as a professional in the academic setting. A large part of this idea is certainly influenced by my interactions and experiences in the Scuzanne Catalina Bartolomucci Research Facility for the Enhancement of f-block Advancements. Music is a large part of my way of keeping sane at work. For a special note, for all that they have done, I will share my eclectic mix of top played artists and bands: Switchfoot, NEEDTOBREATHE, kishibashi, Carly Rae Jepsen, insaneintherainmusic (Carlos Eiene), Amy Grant, Jars Of Clay, Kara Comparetto, and many more. Finally, I would like to recognize all of the organizations which helped secure funding during my time at Purdue. Purdue University (teaching assistantships, Throckmorton Scholarship, SURF Graduate Mentor Award, Bilsland Fellowship), National Science Foundation (CHE-1149875, CAREER grant to Suzanne C Bart; CHE-1625543, MRI 7 program; 1665170, grant to SCB; CHE-1039689, Ill. St. Univ. funding for diffractometer), Department of Energy (Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences Heavy Element Chemistry program through grants DE- SC0008479 to SCB). 8 TABLE OF CONTENTS LIST OF TABLES ............................................................................................................ 11 LIST OF FIGURES .......................................................................................................... 12 ABSTRACT ...................................................................................................................... 15 SYNTHESIS AND REACTIVITY OF URANIUM(III) BENZYL COMPOUNDS ................................................................................................................. 17 1.1 Abstract ................................................................................................................. 17 1.2 Introduction ........................................................................................................... 18 1.3 Experimental ......................................................................................................... 20 1.3.1 General Considerations .................................................................................. 20 1.3.2 General synthesis for Tp*2U(III) alkyl compounds. ...................................... 22 1.3.3 Synthesis of Tp*2U(N3) (3-N3). ....................................................................
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