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Dissertation Reactivity and Selectivity in The DISSERTATION REACTIVITY AND SELECTIVITY IN THE POLYMERIZATION OF MULTIFUNCTIONAL ACRYLIC MONOMERS BY CHIRAL ZIRCONOCENIUM CATALYSTS Submitted by Fernando Vidal Peña Department of Chemistry In partial fulfillment of the requirements For the Degree of Doctor of Philosophy Colorado State University Fort Collins, Colorado Summer 2017 Doctoral Committee: Advisor: Eugene Y.-X. Chen Richard G. Finke Steven Strauss Ellen Fisher David Wang Copyright by Fernando Vidal Peña 2017 All Rights Reserved ABSTRACT REACTIVITY AND SELECTIVITY IN THE POLYMERIZATION OF MULTIFUNCTIONAL ACRYLIC MONOMERS BY CHIRAL ZIRCONOCENIUM CATALYSTS Described in this dissertation are the results of investigating the reactivity and selectivity in the polymerization of multifunctional acrylic monomers by chiral cationic zirconocenium catalysts. The unprecedented precision polymer synthesis method developed in this workthe polymerization of polar divinyl monomers that is not only living but also simultaneously chemoselective and stereoselectivehas enabled the synthesis of well-defined highly stereoregular functionalized polymers bearing reactive C=C bonds on every chiral repeat unit. Thus, under ambient conditions, chiral ansa-ziroconocenium catalysts of the appropriate symmetry (C2- vs CS-ligated) have afforded highly isotactic and highly syndiotactic double-bond- carrying polymers, respectively, with controlled molecular weights and narrow dispersities. The enantiomorphic-site controlled, conjugate-addition coordination polymerization mechanism is responsible for the observed high degree of control over the polymerization characteristics, chemoselectivity and stereochemistry. Soft-material applications of such stereoregular and reactive ene-bearing polymers have also explored, including chemical post-functionalization to functional materials, photocuring to elastic films, and molecular recognition to robust crystalline supramolecular stereocomplexes and helical C60 inclusion complexes. A class of important biorenewable monomers containing one methacrylic C=C and two ester groups, namely itaconic esters and anhydride, have been examined, for the first time, for their ii polymerizability towards both neutral and cationic bridged ansa-zirconocenes and nonbridged zirconocenes. This investigation has yielded a fundamental understanding of the reactivity of the zirconocene complexes towards such monomers, specifically the fundamental chain initiation and propagation steps, structures of resting metallocyclic chelates, as well as kinetic and thermodynamic intermediates. iii DEDICATION To Carmen Marqués Gil and Elena Pezzi Martínez, those tenderhearted giants upon whose shoulders I stood for the first time and whose life lessons will walk with me forever. A Carmen Marqués Gil y Elena Pezzi Martínez, aquellas cariñosas gigantes sobre cuyos hombros me alcé por primera vez y cuyas lecciones vitales caminarán conmigo por siempre. iv TABLE OF CONTENTS ABSTRACT .................................................................................................................................... ii DEDICATION ............................................................................................................................... iv CHAPTER 1 – Introduction ....................................................................................................... 1 CHAPTER 2 – Chemoselective, Stereospecific, and Living Polymerization of Polar Divinyl Monomers by Chiral Zirconocenium Catalysts 2.1. Summary ................................................................................................................. 5 2.2. Introduction ............................................................................................................. 6 2.3. Results and Discussion ........................................................................................... 8 2.4. Conclusions ........................................................................................................... 31 REFERENCES ............................................................................................................................. 34 CHAPTER 3 – Robust Crosslinked Stereocomplexes and C60 Inclusion Complexes of Vinyl- Functionalized Stereoregular Polymers Derived from Chemo/Stereoselective Coordination Polymerization 3.1. Summary ............................................................................................................... 38 3.2. Introduction ........................................................................................................... 39 3.3. Results and Discussion ......................................................................................... 43 3.4. Conclusions ........................................................................................................... 71 REFERENCES ............................................................................................................................. 74 v CHAPTER 4 – Reactivity of Bridged and Nonbridged Zirconocenes towards Biorenewable Itaconic Esters and Anhydride 4.1. Summary ............................................................................................................... 80 4.2. Introduction ........................................................................................................... 81 4.3. Results and Discussion ......................................................................................... 84 4.4. Conclusions ......................................................................................................... 107 REFERENCES ........................................................................................................................... 109 CHAPTER 5 – Precision Polymer Synthesis via Chemoselective, Stereoselective, and Living/Controlled Polymerization of Polar Divinyl Monomers 5.1. Summary ............................................................................................................. 112 5.2. Introduction ......................................................................................................... 112 5.3. Metal-Catalyzed Coordination-Addition Polymerization of Polar Divinyl Monomers ............................................................................................................ 116 5.4. Organocatalyzed Conjugate-Addition Polymerization of Polar Divinyl Monomers ........................................................................................................... 125 5.5. Post-Functionalization of Vinyl-Containing Stereoregular Polymers ................ 130 5.6. Conclusions and Outlook .................................................................................... 133 REFERENCES ........................................................................................................................... 134 APPENDIX A – Experimental Details and Supporting Information for Chapter 2 A.1. Materials, Reagents, and Methods ...................................................................... 140 A.2. Additional Figures and Tables ............................................................................ 156 A.3. References ........................................................................................................... 174 vi APPENDIX B – Experimental Details and Supporting Information for Chapter 3 B.1. Materials, Reagents, and Methods ...................................................................... 175 B.2. Additional Figures and Tables ............................................................................ 189 B.3. Computational Details ........................................................................................ 201 B.4. References ........................................................................................................... 228 APPENDIX C – Experimental Details and Supporting Information for Chapter 4 C.1. Materials, Reagents, and Methods ...................................................................... 230 n + − + C.2. Crystal Structure Report for [Cp*( PrCp)Zr(HNMe2)=NMe2] [B(C6F5)4] (9 ) 256 C.3. Additional Figures .............................................................................................. 265 C.4. References ........................................................................................................... 310 vii CHAPTER 1 Introduction The dissertation presented hereinafter was conceived in a “journals-format” style, in agreement with the Graduate School guidelines at Colorado State University, and it contains four manuscripts. Three of the manuscripts have already been published in peer-reviewed chemistry journals, including two full-paper articles in the Journal of the American Chemical Society and one invited account article in Synlett, while the fourth manuscript has been completely prepared and submitted to Organometallics. The purpose of this dissertation work is to utilize the readily available chiral ansa-zirconocenes as catalysts to polymerize challenging multifunctional polar vinyl monomers, since their successful chemoselective and stereoselective polymerization would produce densely functionalized and stereoregular materials with interesting mechanical and physical properties. However, significant challenges exist in such cases as polymerization incompatibilities may arise either from the inability of the chiral catalyst to distinguish between two polymerizable groups or the presence of a competing functional group in the monomer chemical structure. The former case is exemplified by
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