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Selective Tripodal Titanium Silsesquioxane Catalysts for the Epoxidation of Unactivated Olefins

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Selective Tripodal Titanium Silsesquioxane Catalysts for the Epoxidation of Unactivated Olefins University of Kentucky UKnowledge Theses and Dissertations--Chemistry Chemistry 2015 SELECTIVE TRIPODAL TITANIUM SILSESQUIOXANE CATALYSTS FOR THE EPOXIDATION OF UNACTIVATED OLEFINS Sarah M. Peak University of Kentucky, [email protected] Right click to open a feedback form in a new tab to let us know how this document benefits ou.y Recommended Citation Peak, Sarah M., "SELECTIVE TRIPODAL TITANIUM SILSESQUIOXANE CATALYSTS FOR THE EPOXIDATION OF UNACTIVATED OLEFINS" (2015). Theses and Dissertations--Chemistry. 52. https://uknowledge.uky.edu/chemistry_etds/52 This Doctoral Dissertation is brought to you for free and open access by the Chemistry at UKnowledge. It has been accepted for inclusion in Theses and Dissertations--Chemistry by an authorized administrator of UKnowledge. For more information, please contact [email protected]. STUDENT AGREEMENT: I represent that my thesis or dissertation and abstract are my original work. Proper attribution has been given to all outside sources. I understand that I am solely responsible for obtaining any needed copyright permissions. I have obtained needed written permission statement(s) from the owner(s) of each third-party copyrighted matter to be included in my work, allowing electronic distribution (if such use is not permitted by the fair use doctrine) which will be submitted to UKnowledge as Additional File. I hereby grant to The University of Kentucky and its agents the irrevocable, non-exclusive, and royalty-free license to archive and make accessible my work in whole or in part in all forms of media, now or hereafter known. I agree that the document mentioned above may be made available immediately for worldwide access unless an embargo applies. I retain all other ownership rights to the copyright of my work. I also retain the right to use in future works (such as articles or books) all or part of my work. I understand that I am free to register the copyright to my work. REVIEW, APPROVAL AND ACCEPTANCE The document mentioned above has been reviewed and accepted by the student’s advisor, on behalf of the advisory committee, and by the Director of Graduate Studies (DGS), on behalf of the program; we verify that this is the final, approved version of the student’s thesis including all changes required by the advisory committee. The undersigned agree to abide by the statements above. Sarah M. Peak, Student Dr. Folami Ladipo, Major Professor Dr. Dong-Sheng Yang, Director of Graduate Studies SELECTIVE TRIPODAL TITANIUM SILSESQUIOXANE CATALYSTS FOR THE EPOXIDATION OF UNACTIVATED OLEFINS DISSERTATION A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the College of Arts and Sciences at the University of Kentucky By Sarah Michelle Peak Lexington, Kentucky Director: Dr. Folami Ladipo, Professor of Chemistry Lexington, Kentucky 2015 Copyright © Sarah Michelle Peak ABSTRACT OF DISSERTATION SELECTIVE TRIPODAL TITANIUM SILSESQUIOXANE CATALYSTS FOR THE EPOXIDATION OF UNACTIVATED OLEFINS Regiomeric mixture of HMe2Si(CH2)3(i-Bu)6Si7O9(OH)3 (6), containing a Si- H group in one of the ligands of the silsesquioxane, was tethered onto a vinyl terminated hyperbranched poly(siloxysilane) polymer via a hydrosilation reaction to generate extremely active catalysts, P1-8 and c-P1-8. The synthesis of 6, in good yield, was accomplished via hydrosilation of CH2=CHCH2(i-Bu)7Si8O12 (1) to generate ClMe2Si(CH2)3(i-Bu)7Si8O12 (3) followed by the reduction of 3 with LiAlH4 to afford HMe2Si(CH2)3(i-Bu)7Si8O12 (4) where the base-catalyzed excision of one framework silicon was employed to generate a regiomeric mixture of 6. [Ti(NMe2){Et3Si(CH2)3(i-Bu)6Si7O12}] (7), [Ti(NMe2){HMe2Si(CH2)3(i- Bu)6Si7O12}] (8), [Ti(NMe2){(i-C4H9)7Si7O12}] (9) and [Ti(NMe2){(c-C6H11)7Si7O12}] (10) were synthesized via protonolysis of Ti(NMe2)4 with one equivalent of the trisilanol precursor in order to determine if the presence of isomers would be intrinsically different as compared to the uniformly substituted catalysts. Isomers 8 and 9, demonstrated lower activity as compared to the uniformly substituted catalysts 9 and 10, however the isomers still exhibited extremely high catalytic activity for the epoxidation of 1-octene using tert-butyl hydroperoxide (TBHP) relative to titanium catalysts used in industry. Additionally, 9, 10, P1-8 and c-P1- 8 were very selective catalysts for the epoxidation of various olefins such as terminal (1-octene), cyclic (cyclohexene or 1-methylcyclohexene), and more demanding olefins (limonene or α-pinene) employing TBHP as the oxidant. Furthermore, P1-8 and c-P1-8 were recyclable with minimal loss of titanium however the catalysts could also be repaired if a loss in activity was observed. Preliminary epoxidation reactions employing P1-8 and c-P1-8 along with hydrogen peroxide (H2O2) as the oxidant were also explored using different solvents. P1-8 degraded quickly due to the hydrolysis of the titanium from the large amount of water present in the reaction mixture however c-P1-8 showed activity for the epoxidation of cyclohexene. Finally, regiomeric mixture of Ti(NMe2)(HS(CH2)3)(i-C4H9)6Si7O12) (13), was tethered onto gold nanoparticles for the conversion of propene to propylene oxide using molecular hydrogen and oxygen. While the catalysts showed low activity under our reaction conditions, numerous improvements can be investigated in order to improve upon the catalysts. Keywords: Olefin epoxidation; Titanium silsesquioxane; Gold nanoparticles; Heterogeneous catalysis; Immobilized catalysts; Non-activated alkenes Sarah Peak July, 21, 2015 SELECTIVE TRIPODAL TITANIUM SILSESQUIOXANE CATALYSTS FOR THE EPOXIDATION OF UNACTIVATED OLEFINS By Sarah Peak Dr. Folami Ladipo Director of Dissertation Dr. Dong-Sheng Yang Director of Graduate Studies July 21, 2015 FOR MY FAMILY ACKNOWLEDGEMENTS I would like to take this opportunity express my gratitude to multiple people who have encouraged, aided, and supported me while I have been in graduate school. First and foremost would be my advisor, Dr. Folami Ladipo, who has guided me taught me how to think critically about solutions and not accepting things at face-value. Additionally, Dr. Mark Crocker has been invaluable to my research by allowing me to test my epoxidation trials on the equipment at CAER and providing solid practical advice about my research. I would also like to thank my additional committee members, Drs. Watson and Knuston for all their support over the course of my stay at the University of Kentucky. Thank you to Tonya Morgan who ran the majority of the GC data for me. Her work was instrumental to the research described herein. In addition, I would like to thank Mr. John Layton for his assistance with NMR spectroscopy as well as Dr. Anne LaPointe for her assistance with GPC. My family and friends also deserves my deepest heartfelt thanks for all their support, love, encouragement, and patience given to me while at UK. Without my family, I would not have been able to accomplish this research and wouldn’t be the person I am today. They have taught me that hard-work eventually pays off and that if you are going to start something, you have to finish it to the best of your ability. I cannot express how grateful I am for my families support. I also need to thank all my colleagues at the University of Kentucky. They have aided me tremendously by encouraging my research endeavors, engaging in discussions that allowed me to think deeper about subjects, as well as borrowing equipment and/or chemicals which were needed for my research. In particular I would like to thank Dr. Anitha Gowda who was a great friend and colleague in Dr. Ladipo’s lab when I first arrived at UK as well as Daudi Saang’onyo who joined our group recently. Finally, I would like to thank my previous professors who have taught me to believe in myself and shoot for the stars. First off, thank you to my advisor iii from Eastern Kentucky University, Dr. Nathan Tice, who encouraged me in my endeavors and even recommended Dr. Ladipo’s group to me. I would also be remise if I didn’t not mention my professors at Georgetown College, Drs. Campbell, Fraley and Wiseman who lit a fire in me for my passion for chemistry. They made the subject come to life and have taught me more than they will ever know. It is because of these professors that I am able to write this dissertation and achieve my goals. Lastly, I would like to thank the National Science Foundation who supported this work through a grant under CHE - 1058097. iv TABLE OF CONTENTS Chapter Page Acknowledgement ........................................................................................... iii List of Tables ................................................................................................... x List of Figures ................................................................................................ xiii List of Schemes ............................................................................................. xxi 1. Introduction ................................................................................................ 1 1.1 Importance ..................................................................................... 1 1.2 Synthetic Methods ......................................................................... 5 1.3 Catalytic Pathways ......................................................................... 8 1.4 Objective and Dissertation Outline ............................................... 23 2. Selective epoxidation of 1-octene
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