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Florida State University Libraries Florida State University Libraries Electronic Theses, Treatises and Dissertations The Graduate School 2017 Non-Aqueous Transuranic Coordination Complexes Shane S. Galley Follow this and additional works at the DigiNole: FSU's Digital Repository. For more information, please contact [email protected] FLORIDA STATE UNIVERSITY COLLEGE OF ARTS AND SCIENCES NON-AQUEOUS TRANSURANIC COORDINATION COMPLEXES By SHANE S. GALLEY A Dissertation submitted to the Department of Chemistry and Biochemistry in partial fulfillment of the requirements for the degree of Doctor of Philosophy 2017 Shane S. Galley defended this thesis on November 13, 2017 The members of the supervisory committee were: Thomas E. Albrecht-Schmitt Professor Directing Dissertation Vladimir Dobrosavljevic University Representative Kenneth Hansom Committee Member Michael Shatruk Committee Member The Graduate School has verified and approved the above-named committee members, and certifies that the dissertation has been approved in accordance with university requirements. ii This is dedicated to my family at Hot Yoga Tallahassee. Thank you for the love and support. May the light in me, Honor the light in you. Namaste iii ACKNOWLEDGMENTS First, I would like to thank my Family. My parents, Kevin and Gia, and Grammy for all the support they provide throughout this journey. Even though you were 1000 miles away, it was comforting knowing you were there when I needed you guys. A huge shout out to my sister Samantha and baby Layla, for all the visits and distractions. Having you guys in the same state this past year was awesome. Thank you for being there though the good and the bad. And Michael, as you have been with me since my second year of grad school. Thank you for all the love, support, and dealing with all my Amanda Bynes/2007 Britney Spears breakdowns. I would like to thank my advisor, Dr. Thomas E. Albrecht-Schmitt. You have given me the support, guidance and amazing opportunities to succeed and be the best I can be. I am sincerely grateful for all that you have done for me. Also, thanks for not throwing me out the fifth story window, that fall wouldn’t have been pleasant. I am very appreciative for all the Schminions that I have gotten to work with over the course of my graduate school career. I would especially like to thank Samantha Cary for being my beacon in the lab and my favorite coffee date. Unfortunately, I will not be following you to Los Alamos. Ali Arico for being on this journey with me from Day 1 but a week late. Of course my lovely undergrads, Cayla, Mia, and Jacob. Thank you for letting me mentor you over the past years and accomplishing some great work! Maybe one day all our ducks will be in a row. A huge shout goes to my academic step parents, Stosh Kozimor and Suzanne Bart. Stosh, for your knowledge/techniques in actinide chemistry along with the lovely nights at the SLAC. Suzanne for collaborating, advising, and challenging my synthetic chemistry of the actinides. Last, I would like to thank Florida State University for allowing me to do this work. The Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, Heavy Elements Chemistry Program, U.S. Department of Energy, under Grant DE-FG02-09ER16026, provided all of the funding for this dissertation. iv TABLE OF CONTENTS List of Tables ................................................................................................................................ vii List of Figures ................................................................................................................................ ix Abstract ........................................................................................................................................ xiii 1. INTRODUCTION ......................................................................................................................1 1.1 Importance of Understanding Actinide Ligand Bonding.....................................................1 1.2 Non-Aqueous Transuranic Chemistry .................................................................................1 1.2.1 Bonding in Actinides ..................................................................................................2 1.2.2 Challenges of Transuranic Non-aqueous Chemistry ..................................................2 1.3 Transuranic Non-Aqueous Coordination Compounds ..........................................................4 1.3.1 Simple Non-Aqueous Coordination Complexes .........................................................4 1.3.2 Air and Moisture Sensitive Non-Aqueous Transuranic Chemistry ............................5 1.4 Thesis Objective ....................................................................................................................7 1.5 Figures ...................................................................................................................................8 2. SYNTHESIS AND STRUCTURES OF TRIS TERPYRIDINE COMPOUNDS OF TRIVALENT LANTHAINDES AND AMERICIUM ..................................................................11 2.1 Introduction ........................................................................................................................11 2.2 Results and Discussion ......................................................................................................11 2.3 Conclusion .........................................................................................................................13 2.4 Experimental ......................................................................................................................13 2.5 Figures................................................................................................................................15 3. SYNTHESIS AND CHARACTERIZATION OF AMERICIUM AND CALIFORNIUM DITHIOCARBAMATES ..............................................................................................................21 3.1 Introduction ........................................................................................................................21 3.2 Results and Discussion ......................................................................................................21 3.3 Conclusion .........................................................................................................................23 3.4 Experimental ......................................................................................................................24 3.5 Figures................................................................................................................................26 4. USING REDOX-ACTIVE LIGANDS TO UNDERSTAND BONDING IN TRIVALENT ACTINIDES ..................................................................................................................................31 4.1 Introduction ........................................................................................................................31 4.2 Results and Discussion ......................................................................................................32 4.3 Conclusion .........................................................................................................................35 4.4 Experimental ......................................................................................................................35 4.5 Figures................................................................................................................................37 v 5. UNDERSTANDING THE SCARCITY OF THORIUM PEROXIDE CLUSTERS ...............44 5.1 Introduction ........................................................................................................................44 5.2 Results and Discussion ......................................................................................................44 5.3 Conclusion .........................................................................................................................46 5.4 Experimental ......................................................................................................................47 5.5 Figures................................................................................................................................47 6. UNCOVERING THE ORIGIN OF DIVERGENCE IN THE CSM(CRO4)2 (M = LA ‒ SM; AM) FAMILY THROUGH BAND STRUCTURE ANALYSIS AND AN EXAMINATION OF THE CHEMICAL BONDING IN A MOLECULAR CLUSTER ......................................49 6.1 Introduction ........................................................................................................................49 6.2 Results and Discussion ......................................................................................................51 6.3 Conclusion .........................................................................................................................57 6.4 Experimental ......................................................................................................................58 6.5 Figures................................................................................................................................61 7. CONCLUSION .........................................................................................................................66 APPENDICES A. TABLES FROM CHAPTER 2 .................................................................................................68 B. TABLES
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