SYNTHESIS AND REACTIONS OF STERICALLY ENCUMBERED INORGANIC AND ORGANOMETALLIC COMPLEXES By Nicholas Charles Boyde Dissertation Submitted to the Faculty of the Graduate School of Vanderbilt University in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY in Chemistry June 30th , 2017 Nashville, Tennessee Approved: Timothy P. Hanusa, Ph. D. Charles M. Lukehart, Ph. D. David W. Wright, Ph. D. James E. Wittig, Ph. D. This work is dedicated to all of the educators who made my journey exciting and enlightening. Thank you. ii ACKNOWLEDGEMENTS There are many individuals that guided me along my scientific career and I would like to briefly acknowledge them. Stephen “Wito” Witowich was instrumental in my education as he inspired my love of chemistry, challenged me to do my best, and was a friend. Although Wito is no longer alive, I constantly remember his teaching style and the energy with which he taught. I hope to inspire the next generation of chemists the way that he inspired me. Scott Mason guided me through my undergraduate career by providing me the foundations of inorganic chemistry, allowing me to design my senior research project, and offering continued guidance in my pursuit of a career in higher education. The success of my graduate career was all thanks to the guidance and tutelage of Timothy Hanusa. My time in Tim’s lab was invaluable as the skills and experience that I gained will remain with me throughout the rest of my life. Tim’s wealth of knowledge was greatly appreciated as I learned a great deal every day and I cannot fully express my gratitude for everything that you have done. I would like to extend a special thanks to Grant Steelman for all of the work that he has contributed to my research. It was a pleasure to work with you throughout your time in lab. Your willingness to work on a variety of projects and learn a variety of techniques made mentoring rewarding. I wish you the best in your future endeavors. A special thanks is also owed to Nathan Schley for assisting with many crystal structures. Without the assistance of Nathan I would not have discovered a key compound for my system iii and therefore might have missed a crucial discovery. His willingness to check crystals that were less than ideal was greatly appreciated. This work was financially supported through the National Science Foundation (CHE- 1112181), The American Chemical Society–Petroleum Research Fund (56027-ND3), a Discovery Grant of Vanderbilt University, and the Mitchum E. Warren, Jr. Graduate Research Fellowship. iv TABLE OF CONTENTS Page DEDICATION ................................................................................................................................ ii ACKNOWLEDGEMENTS ........................................................................................................... iii LIST OF TABLES ........................................................................................................................ vii LIST OF FIGURES ..................................................................................................................... viii COMMON ABBREVIATIONS AND SYMBOLS ........................................................................x Chapter 1. Formation of sterically encumbered molecules to study steric and electronic effects ................1 1.1 Introduction ...........................................................................................................................1 1.2 Reaction conditions toward product formation .....................................................................2 1.3 Bulky ligands .........................................................................................................................4 1.3.1 Amides .............................................................................................................................5 1.3.2 Allyls ...............................................................................................................................5 1.4 Steric and electronic effects ..................................................................................................6 1.5 Methods Employed................................................................................................................7 1.6 Conclusion .............................................................................................................................8 2. Structural Distortions in M[E(SiMe3)2]3 Complexes (M = Group 15, f element, E = N, CH) ....9 2.1 Introduction ...........................................................................................................................9 2.2 Results and Discussion ........................................................................................................11 2.3 Conclusion ...........................................................................................................................35 2.4 Experimental .......................................................................................................................36 3. Preparation of substituted P[N(SiMe3)2]3 complexes and nanoparticle applications .....42 3.1 Introduction .........................................................................................................................42 3.2 Results and Discussion ........................................................................................................44 3.2.1 Nanoparticle formation ..................................................................................................44 v 3.2.2 Derivatives of P[N(SiMe3)2]3 .......................................................................................47 3.3 Conclusion ...........................................................................................................................50 3.4 Future Directions .................................................................................................................51 3.5 Experimental .......................................................................................................................52 4. Reaction environment and ligand liability in group 4 Cp2MXY (X,Y = Cl, OtBu) ..................56 4.1 Introduction .........................................................................................................................56 4.2 Results and Discussion ........................................................................................................57 4.3 Conclusion ...........................................................................................................................67 4.3 Experimental .......................................................................................................................68 5. Multicomponent mechanochemical synthesis of cyclopentadienyl titanium alkoxy halides ....74 5.1 Introduction .........................................................................................................................74 5.2 Results and Discussion ........................................................................................................76 5.3 Conclusion ...........................................................................................................................91 5.4 Experimental .......................................................................................................................91 6. Symmetric assembly of a sterically encumbered allyl complex: mechanochemical and solution synthesis of the tris(allyl)beryllate, K[BeA′](A′ = 1,3-(SiMe₃)₂C₃H₃) ....................................96 6.1 Introduction .........................................................................................................................96 6.2 Results and Discussion ........................................................................................................98 6.3 Conclusion .........................................................................................................................108 6.4 Experimental .....................................................................................................................109 Appendix A1. Crystallographic and spectral data of Group 15 M[N(SiMe3)2]3 ..........................................113 A2. Nanoparticle formation from P[N(SiMe3)2]3 and NMR spectra of attempted derivatives ...122 A3. Crystallographic and fractional coordinates of mixed ligand group 4 species .....................128 A4. Crystallographic data of K[Be(1,3-(SiMe3)2C3H3)3] ............................................................147 REFERENCES ............................................................................................................................148 vi LIST OF TABLES Table 1 Selected bond distances, angles, and Gsolid values in representative M[N(SiMe3)2]3 complexes.. .................................................................................................................... 17 Table 2 Selected bond distances, angles, and Gsolid values in representative M[CH(SiMe3)2]3 complexes.. .................................................................................................................... 23 Table 3 Selected Experimental and UFF Optimized Bond Distances and Angles for Pu[N(SiMe3)2]3, Ce[CH(SiMe3)2]3, and Sb[N(SiMe3)2]3............................................... 27 Table 4. Selected experimental and DFT optimized bond distances and angles for E[N(SiMe3)2]3 (E = P–Bi).. ...................................................................................................................