UNIVERSITY OF MISSOURI, COLUMBIA Synthesis and Reactivity of Actinide Phosphorano-Stabilized Carbene and Phosphido Complexes DISSERTATION Submitted in partial satisfaction of the requirements For the degree of DOCTOR OF PHILOSOPHY in Chemistry by Pokpong Rungthanaphatsophon University of Missouri, Columbia May 2018 Portions of Chapter 1 © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Portions of Appendix A © 2016 Royal Society of Chemistry All other materials © 2018 Pokpong Rungthanaphatsophon The dissertation of Pokpong Rungthanaphatsophon is approved and is acceptable in quality and form for publication on microfilm and digital formats: __________________________________ __________________________________ __________________________________ __________________________________ Committee Chair Acknowledgements I would like to thank my advisor, Justin Walensky, for the guidance and mentorship he provided. Charles Barnes, Wei Wycoff, and Steven Kelley for their technical support at the University of Missouri-Columbia. The computational portion of this dissertation would not be possible without the help of Adrien Bathelier, Ludovic Castro, Patrick Huang, Laurent Maron, Thomas Duignan, Jochen Autschbach, Enrique Batista, and Ping Yang. Special thanks to the Walensky group: Robert Ward, Matthew Vollmer, Andrew Lane, Andrew Behrle, Andrew Breshears, Kira Behm, Sean Vilanova, Alex Myers, Michael Tarlton, and Michael Murray. ii Table of Contents Acknowledgements ............................................................................................................. ii Table of Figures ................................................................................................................. vi Table of Tables ....................................................................................................................x Abstract of Dissertation .......................................................................................................1 Introduction ..........................................................................................................................3 Chapter 1: Formation of Methane vs. Benzene in the Reactions of (C5Me5)2Th(CH3)2 with [CH3PPh3]X, X = Cl, Br, I, Yielding Thorium-Carbene or Thorium-Ylide Complexes ...........................................................................................................................8 Introduction .................................................................................................................................. 8 Experimental .............................................................................................................................. 10 General Considerations. ......................................................................................................... 10 Crystal structure determination and refinement. .................................................................... 13 Computational details. ........................................................................................................... 14 Results and Discussion .............................................................................................................. 15 Density Functional Theory (DFT) and Mechanistic Investigations ....................................... 18 Conclusion ................................................................................................................................. 24 Chapter 2: Phosphorano-Stabilized Carbene Complexes with Short Thorium(IV) and Uranium(IV)-Carbon Bonds ...................................................................................26 Introduction ................................................................................................................................ 26 iii Experimental .............................................................................................................................. 27 General Considerations. ......................................................................................................... 27 Crystal structure determination and refinement. .................................................................... 31 Computational Details. .......................................................................................................... 32 Results and Discussion .............................................................................................................. 33 Syntheses. .............................................................................................................................. 33 Spectroscopy. ......................................................................................................................... 34 Structural Analysis. ................................................................................................................ 35 Electronic Structure Calculations........................................................................................... 37 Conclusion ................................................................................................................................. 44 Chapter 3: Four Electron Reduction Chemistry Using an Uranium(III) Phosphido Complex ............................................................................................................................46 Introduction ................................................................................................................................ 46 Experimental .............................................................................................................................. 47 General Considerations .......................................................................................................... 47 Crystallographic data collection and structure determination ................................................ 50 Result and discussion. ................................................................................................................ 53 Conclusions ................................................................................................................................ 57 Chapter 4: Influence of Substituents on Electronic Structure of Mono- and Bis(Phosphido) Thorium(IV) Complexes ......................................................................58 Introduction ................................................................................................................................ 58 iv Experimental .............................................................................................................................. 59 General considerations. .......................................................................................................... 59 Computational Details. .......................................................................................................... 65 Crystal structure determination and refinement. .................................................................... 65 Results and Discussion .............................................................................................................. 68 Syntheses. .............................................................................................................................. 68 Structural Analysis. ................................................................................................................ 70 Spectroscopy and TD-DFT Calculations. .............................................................................. 74 Conclusion ................................................................................................................................. 79 Appendix A: Copper(I) Clusters with Bulky Dithiocarboxylate, Thiolate, and Selenolate Ligands ...........................................................................................................81 Introduction ................................................................................................................................ 81 Experimental .............................................................................................................................. 82 General Considerations. ......................................................................................................... 82 Appendix B: Reactivity of U(IV) Phosphido Complexes with Organic Azide and Isocyanide. ......................................................................................................................112 Introduction .............................................................................................................................. 112 Experimental Section ............................................................................................................... 112 General Considerations. ....................................................................................................... 112 References .......................................................................................................................125 Vita ..................................................................................................................................157 v Table of Figures Figure 1-1. Phosphorano-stabilized carbene ligands previously used with thorium and/or uranium. .............................................................................................................................. 9 Figure 1-2. Thermal ellipsoid plots of 2 (left) and 3 (right) shown at the 50% probability level.