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SYNTHESIS-AIDED CALCULATIONS by Laura Kathryn Engerer

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SYNTHESIS-AIDED CALCULATIONS by Laura Kathryn Engerer INVESTIGATIONS OF NON-COVALENT BONDING: SYNTHESIS-AIDED CALCULATIONS By Laura Kathryn Engerer 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 May, 2017 Nashville, Tennessee Approved: Date: __________________________________ _________________________ Timothy P. Hanusa, Ph.D., Chair __________________________________ _________________________ Charles M. Lukehart, Ph.D. __________________________________ _________________________ David W. Wright , Ph.D. __________________________________ _________________________ D. Greg Walker, Ph.D. to God, with whom all things are possible ii ACKNOWLEGEMENTS This work would not have been possible without the financial support of Vanderbilt University, the National Science Foundation, and the Petroleum Research Fund–ACS. I also am indebted to Dr. Timothy Hanusa who has stuck with me and given me so much help through this whole process. Finally, thanks must be given to the Psychological & Counseling Center of Vanderbilt University who helped me get through my first two years of depression and quickly back on track to finishing this. Critical to the completion of this document is my sister Carolyn whose editing skills, support, and encouragement to keep on track were more than any sister could hope for. Thanks also to my parents, other sister, friends and family who believed in me. iii TABLE OF CONTENTS Page DEDICATION .................................................................................................................... ii ACKNOWLEDGEMENTS ............................................................................................... iii LIST OF TABLES ............................................................................................................. vi LIST OF FIGURES .......................................................................................................... vii LIST OF ABBREVIATIONS ............................................................................................ ix Chapters 1. INTRODUCTION ...............................................................................................................1 2. A DENSITY FUNCTIONAL THEORY INVESTIGATION OF CATION-Π INTERACTIONS ...........7 Geometric Effects in Olefinic Cation-π Interactions with Alkali Metals ................7 Introduction ........................................................................................................7 Computational methods .....................................................................................8 Results and discussion .....................................................................................10 Isolated double and triple bonds ..........................................................10 Constrained double bonds ....................................................................14 [3,6-M(cyclonona-1,4,7-triene)]+ .....................................................15 Substituted arenes ................................................................................18 Evaluation of angular dependence .......................................................19 Conclusions ......................................................................................................22 Asymmetric Cation-π Interactions .........................................................................22 Introduction ......................................................................................................22 Results and discussion .....................................................................................26 2 + The [K(18-crown-6)(η -C6H6)2] system .............................................27 Constrained systems.............................................................................31 Non-centered cation-π binding modes .................................................32 Conclusion .......................................................................................................36 3. - VS. Π-BONDING IN MANGANESE(II) ALLYL COMPLEXES ..........................................37 Introduction ............................................................................................................37 A´2Mn(thf)2 (3) ................................................................................................39 iv A´´2Mn(tmeda) (4) ...........................................................................................40 Results ....................................................................................................................41 Formation of allyl manganese complexes ........................................................41 Solution magnetic susceptibility measurements ..............................................42 Solid state structure ..........................................................................................42 Computational results ......................................................................................45 Discussion ..............................................................................................................50 Conclusions ............................................................................................................53 Experimental Section .............................................................................................54 General considerations .....................................................................................54 Materials ..........................................................................................................54 Magnetic measurements...................................................................................54 Synthesis of K2MnA’4......................................................................................55 General procedures for X-ray crystallography ................................................55 Computational details ......................................................................................56 4. INVESTIGATION OF CLASSIC UNUSUAL STRUCTURES WITH NEW DFT FUNCTIONALS CONTAINING DESCRIPTIONS OF DISPERSION FORCES ..........................................................58 Introduction ............................................................................................................58 Use of dispersion-corrected functionals in the computational investigation of group 2 and 14 organometallic compounds .....................................................66 Computational method and details...................................................................68 Results of DFT Calculations ..................................................................................69 3-iPr 4-Me Computations and structure of PbCp 2 and PbCp 2 .................................69 Computations and structures of group 2 complexes ........................................77 Decamethylcalcocene ..........................................................................78 Decamethylstrontocene ........................................................................81 Decamethylbariocene ...........................................................................83 Decamethylmagnesocene .....................................................................86 Previous calculations of decamethylstrontocene .............................................87 Computational artifacts from DFT theory .......................................................93 Computations and structural analysis of Ca(C(SiMe3)3)2 ................................95 Conclusions ............................................................................................................99 APPENDICES .................................................................................................................100 Supplementary Material .......................................................................................100 REFERENCES ................................................................................................................109 v LIST OF TABLES Table .............................................................................................................................. Page Chapter 2 1. Interaction energies for [M(C6H6)]+ (C6v) .....................................................................10 + 2. Calculated energies for [M(C2H4)n] .............................................................................13 + 3. Calculated energies for [M(C2H2)n] .............................................................................14 4. Calculated energies for complexes with constrained double bonds ..............................17 5. Calculated energies (∆H°) for [M(3,6-cyclonona-1,4,7-triene)]+ ...............................18 6. Calculated energies (∆H°) for substituted systems ........................................................18 Chapter 3 1. Selected Distances and Angles for 3 (A´2Mn(thf)2) ......................................................57 2. Selected Distances and Angles for 4 (A´´2Mn(tmeda)) .................................................57 3. Selected Distances and Angles for 5 (K2MnA´4) ...........................................................57 Chapter 4 3-iPr 1 The properties of referenced calculations of the PbCp 2 molecule.............................70 4-Me 2 The properties of referenced calculations of the PbCp 2 molecule ............................76 3 The properties of referenced calculations of the CaCp*2 molecule ................................79
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