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Mechanism and Kinetics of Homogeneous Catalysis Silei Xiong Purdue University Purdue University Purdue e-Pubs Open Access Dissertations Theses and Dissertations Spring 2015 Mechanism and kinetics of homogeneous catalysis Silei Xiong Purdue University Follow this and additional works at: https://docs.lib.purdue.edu/open_access_dissertations Part of the Chemical Engineering Commons Recommended Citation Xiong, Silei, "Mechanism and kinetics of homogeneous catalysis" (2015). Open Access Dissertations. 595. https://docs.lib.purdue.edu/open_access_dissertations/595 This document has been made available through Purdue e-Pubs, a service of the Purdue University Libraries. Please contact [email protected] for additional information. Graduate School Form 30 Updated 1/15/2015 PURDUE UNIVERSITY GRADUATE SCHOOL Thesis/Dissertation Acceptance This is to certify that the thesis/dissertation prepared By Silei Xiong Entitled Mechanism and Kinetics of Homogeneous Catalysis For the degree of Doctor of Philosophy Is approved by the final examining committee: James M. Caruthers Chair W. Nicholas Delgass Kendall T. Thomson Mahdi M. Abu-Omar To the best of my knowledge and as understood by the student in the Thesis/Dissertation Agreement, Publication Delay, and Certification Disclaimer (Graduate School Form 32), this thesis/dissertation adheres to the provisions of Purdue University’s “Policy of Integrity in Research” and the use of copyright material. Approved by Major Professor(s): James M. Caruthers Approved by: John Morgan 4/17/2015 Head of the Departmental Graduate Program Date i MECHANISM AND KINETICS OF HOMOGENEOUS CATALYSIS A Dissertation Submitted to the Faculty of Purdue University by Silei Xiong In Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy May 2015 Purdue University West Lafayette, Indiana ii For my parents iii ACKNOWLEDGEMENTS I would like to thank my research advisors, Professor James M. Caruthers, Professor W. Nicholas Delgass, and Professor Kendall T. Thomson for their tremendous support and guidance over the years. Thanks must also be given to the single-site polymerization group from the School of Chemical Engineering: Dr. Grigori A. Medvedev and Jeffrey Switzer, as well as, my collaborators from the Chemistry Department: David Keith Steelman, Thilina N. Gunasekara, and Paul D. Pletcher. This research was financially supported by grants from the United States Department of Energy. iv TABLE OF CONTENTS Page LIST OF TABLES ............................................................................................................ vii LIST OF FIGURES ........................................................................................................... ix ABSTRACT ................................................................................................................ xxxvii CHAPTER 1. INTRODUCTION ...................................................................................... 1 CHAPTER 2. EFFECTS OF PENDANT LIGAND BINDING AFFINITY ON CHAIN TRANSFER FOR 1-HEXENE POLYMERIZATION CATALYZED BY SINGLE-SITE ZIRCONIUM AMINE BIS-PHENOLATE COMPLEXES ............................................... 4 2.1 Introduction .......................................................................................................... 4 2.2 Experimental Procedure ....................................................................................... 9 2.3 Results ................................................................................................................ 14 2.4 Discussion ........................................................................................................... 29 2.5 Conclusions ........................................................................................................ 35 CHAPTER 3. COMPARISON OF SELECTED ZIRCONIUM AND HAFNIUM AMINE BIS(PHENOLATE) CATALYSTS FOR 1-HEXENE POLYMERIZATION ................. 40 3.1 Introduction ........................................................................................................ 40 3.2 Experimental Procedure ..................................................................................... 43 3.3 Results ................................................................................................................ 48 3.4 Discussion ........................................................................................................... 54 3.5 Conclusions ........................................................................................................ 56 CHAPTER 4. EFFECTS OF ELECTRONIC PERTURBATIONS ON 1-HEXENE POLYMERIZATION CATALYZED BY ZIRCONIUM AMINE BIS-PHENOLATE COMPLEXES ................................................................................................................... 59 4.1 Introduction ........................................................................................................ 59 v Page 4.2 Experimental Procedure ..................................................................................... 62 4.3 Results ................................................................................................................ 64 4.4 Discussion ........................................................................................................... 69 4.5 Conclusions ........................................................................................................ 72 CHAPTER 5. SELECTIVE DEGENERATIVE BENZYL GROUP TRANSFER IN OLEFIN POLYMERIZATION ........................................................................................ 76 5.1 Introduction ........................................................................................................ 76 5.2 Experimental Procedure ..................................................................................... 81 5.3 Results ................................................................................................................ 85 5.4 Discussion ........................................................................................................... 98 5.5 Conclusions ...................................................................................................... 102 CHAPTER 6. SIMULTANEOUS POLYMERIZATION AND OLIGOMERIZATION OF 1-HEXENE BY A GROUP IV BIS-PHENOLATE AMINE COMPLEX............... 106 6.1 Experimental Results ........................................................................................ 106 6.2 Kinetic Analysis. .............................................................................................. 113 6.2.1 Oligomerization ........................................................................................ 113 6.2.2 Polymer Formation ................................................................................... 114 6.3 Conclusions ...................................................................................................... 120 CHAPTER 7. ZWITTERIONIC RING-OPENING POLYMERIZATION: MODELS FOR KINETICS OF CYCLIC POLY(CAPROLACTONE) SYNTHESIS ................... 121 7.1 Introduction ...................................................................................................... 121 7.2 Results and Discussion. .................................................................................... 124 7.3 Kinetics Models. ............................................................................................... 127 7.4 Conclusion ........................................................................................................ 145 7.5 Experimental ..................................................................................................... 145 CHAPTER 8. NON-HEME MANGANESE CATALYSTS FOR ON-DEMAND PRODUCTION OF CHLORINE DIOXIDE IN WATER AND UNDER MILD CONDITIONS ................................................................................................................ 156 8.1 Introduction ...................................................................................................... 156 vi Page 8.2 Results .............................................................................................................. 159 8.3 Discussion ......................................................................................................... 167 8.4 Conclusions ...................................................................................................... 174 CHAPTER 9. CONCLUSION ....................................................................................... 179 APPENDICES Appendix A Modeling Methods ............................................................................. 181 Appendix B Supporting Information for Chapter 2 ............................................... 183 Appendix C Supporting Information for Chapter 3 ............................................... 210 Appendix D Supporting Information for Chapter 4 ............................................... 235 Appendix E Supporting Information for Chapter 5 ............................................... 239 Appendix F Supporting Information for Chapter 7 ............................................... 260 Appendix G Supporting Information for Chapter 8 ............................................... 264 VITA ............................................................................................................................... 268 PUBLICATIONS ............................................................................................................ 269 vii LIST OF TABLES Table .............................................................................................................................
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