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Ruthenium-Based Olefin Metathesis Catalysts Bearing Ph-Responsive Ligands: External Control of Catalyst Solubility and Activity" (2011)

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Ruthenium-Based Olefin Metathesis Catalysts Bearing Ph-Responsive Ligands: External Control of Catalyst Solubility and Activity The University of Southern Mississippi The Aquila Digital Community Dissertations Spring 5-2011 Ruthenium-Based Olefin Metathesis Catalysts Bearing pH- Responsive Ligands: External Control of Catalyst Solubility and Activity Shawna Lynn Balof University of Southern Mississippi Follow this and additional works at: https://aquila.usm.edu/dissertations Part of the Chemistry Commons Recommended Citation Balof, Shawna Lynn, "Ruthenium-Based Olefin Metathesis Catalysts Bearing pH-Responsive Ligands: External Control of Catalyst Solubility and Activity" (2011). Dissertations. 693. https://aquila.usm.edu/dissertations/693 This Dissertation is brought to you for free and open access by The Aquila Digital Community. It has been accepted for inclusion in Dissertations by an authorized administrator of The Aquila Digital Community. For more information, please contact [email protected]. The University of Southern Mississippi RUTHENIUM-BASED OLEFIN METATHESIS CATALYSTS BEARING PH-RESPONSIVE LIGANDS: EXTERNAL CONTROL OF CATALYST SOLUBILITY AND ACTIVITY by Shawna Lynn Balof Abstract of a Dissertation Submitted to the Graduate School of The University of Southern Mississippi in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy May 2011 ABSTRACT RUTHENIUM-BASED OLEFIN METATHESIS CATALYSTS BEARING PH-RESPONSIVE LIGANDS: EXTERNAL CONTROL OF CATALYST SOLUBILITY AND ACTIVITY by Shawna Lynn Balof May 2011 Sixteen novel, Ru-based olefin metathesis catalysts bearing pH responsive ligands were synthesized. The pH-responsive groups employed with these catalysts included dimethylamino (NMe2) modified NHC ligands as well as N-donor dimethylaminopyridine (DMAP) and 3-(o-pyridyl)propylidene ligands. These pH- responsive ligands provided the means by which the solubility and/or activity profiles of the catalysts produced could be controlled via acid addition. The main goal of this dissertation was to design catalyst systems capable of performing ring opening metathesis (ROMP) and ring closing metathesis (RCM) reactions in both organic and aqueous media. In an effort to quickly gain access to new catalyst structures, a template synthesis for functionalized NHC ligand precursors was designed, in addition to other strategies, to obtain ligand precursors with ancillary NMe2 groups. Kinetic studies for the catalysts produced from these precursors showed external control of catalyst solubility was afforded via protonation of the NMe2 groups of their NHC ligands. Additionally, this protonation afforded external control of catalyst propagation rates for several catalysts. This is the first known independent external control for the propagation rates of ROMP catalysts. The incorporation of pH-responsive N-donor ligands into catalyst structures also provided the means for the external control of metathesis activity, as the protonation of these ligands resulted in an increased initiation rate based on their fast and ii irreversible dissociation from the metal center. The enhanced external control makes these catalysts applicable to a wide range of applications, some of which have been explored by us and/or through collaboration. Three of the catalysts designed showed remarkable metathesis activity in aqueous media. These catalysts displayed comparable RCM activity in aqueous media to a class of water-soluble catalysts reported by Grubbs et al., considered to be the most active catalyst for aqueous olefin metathesis reactions. In ROMP reactions these particular catalysts dramatically outperformed the literature catalysts, accomplishing ROMP full conversion rates within 15 minutes compared to several hours observed with the literature catalyst. These catalysts were also able to accomplish these reactions at lower catalyst loadings than ever reported with the literature catalyst, making them the most active aqueous olefin metathesis catalysts to date. iii COPYRIGHT BY SHAWNA LYNN BALOF 2011 The University of Southern Mississippi RUTHENIUM-BASED OLEFIN METATHESIS CATALYSTS BEARING PH-RESPONSIVE LIGANDS: EXTERNAL CONTROL OF CATALYST SOLUBILITY AND ACTIVITY by Shawna Lynn Balof A Dissertation Submitted to the Graduate School of The University of Southern Mississippi in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy Approved: Hans Schanz________________________ Director Douglas Masterson__________________ Wujian Miao________________________ Sarah Morgan_______________________ Karl Wallace________________________ Susan A. Siltanen____________________ Dean of the Graduate School May 2011 ACKNOWLEDGMENTS I would like to thank my advisor and chair of my committee, Dr. Hans Schanz, as well as the other committee members, Dr. Douglas Masterson, Dr. Wujian Miao, Dr. Sarah Morgan, and Dr. Karl Wallace, for their advice and support throughout the duration of this project. I would especially like to thank Dr. Hans Schanz for his enormous patience and commitment to this project. Special thanks go to the many collaborators of the Schanz research group, including Dr. Andrew Lowe, Dr. Edward Valente, Dr. Steven P’Pool, Dr. Allan Schiller, Dr. Bing Yu, Dr. Yan Ling, Dr. Yong Zhang, Dr. Kevin Müller, and Dr. Andrea Robinson. I want to express special thanks to the undergraduate students, including David Hudson, Adam Roberts, Miles Dunbar, Samantha Odom, and Allie Carpenter, who have contributed greatly to the synthesis of the compounds explored in this dissertation. Appreciation is also expressed to the Department of Chemistry and Biochemistry at The University of Southern Mississippi for giving me this great opportunity. For funding I would like to thank the Trent Lott Center for Innovation, whose Innovation Award helped to fund my second year in graduate school. I would also like to thank BASF for providing the funding that has carried our research group for the past two years. Finally, I would like to thank my friends and family. In particular my husband, our children, and my father, for the endless encouragement and many sacrifices they have made in order to allow me to study here. iv TABLE OF CONTENTS ABSTRACT …………………….…………………………………..…………………………….ii ACKNOWLEDGMENTS ……………………………………………………………………….iv LIST OF TABLES ………………………………………………………………………………vii LIST OF ILLUSTRATIONS …………………………………………………………………...viii LIST OF SCHEMES ……………………………………………………………………………xi CHAPTER I. INTRODUCTION, BACKGROUND, AND LITERATURE REVIEW FOR OLEFIN METATHESIS AND OLEFIN METATHESIS CATALYSTS ………………………………………….……...1 Introduction ……………………………………………………………………..1 Background and Literature Review …….……………………………………2 Dissertation Goals ……………………………………………………………27 II. NHC LIGAND PRECURSOR SYNTHESIS………………….…………..…28 NHC Ligand Precursors Modified With pH-Responsive Dimethylamino Groups……………………………………...............28 Synthesis of the H2ITap∙HCl and ITap∙HCl Ligand Precursors….............29 Ligand Precursors Using a Template Synthesis………………………......31 III. CATALYST SYNTHESIS…………………………………………………….36 Ru-Based Olefin Metathesis Catalysts Bearing pH-Responsive Ligands ..………………………………………………………………36 Synthesis of Catalysts Bearing pH-Responsive Ligands ………………...37 Summary ………………………………………………………………………53 IV. KINETIC STUDIES IN ORGANIC MEDIA ……………………….……..….54 Substrates and Methods for Relative Kinetic Studies in Organic Media ………………………………………………………………….54 Kinetic Studies ………………………………………………………………..57 Summary ………………………………………………………………………81 V. KINETIC STUDIES IN ACIDIC PROTIC MEDIA ………………………….84 Substrates and Methods for Relative Kinetic Studies in Acidic Protic Media ...………………………………………………………..84 Kinetic Studies ………………………………………………………………..85 Summary ………………………………………………………………………94 v VI. APPLICATIONS FOR OLEFIN METATHESIS CATALYSTS WITH PH-RESPONSIVE LIGANDS ………………………………………..96 VII. SUMMARY …………………………………………………………………..103 VIII. EXPERIMENTALS ………………………………………………………….110 General Procedures ………………………………………………………..110 Materials and Methods ……………………………………………………..111 REFERENCES .………………………………………………………………………………142 vi LIST OF TABLES Table 1. Selected Bond Angles [°] and Distances [Å] for Catalysts 61 and 62 ……...40 2. Selected Bond Angles [°] and Distances [Å] for Catalyst 81 and 83 ….……51 3. GPC Results for ROMP Polymers (Poly-89) From TsOH Studies ……..……62 4. DFT-Calculated Mulliken Atomic Charges at the Ru-Center for Model Complexes ………………………………………………………………………...65 5. RCM of DEDAM With Catalysts 12 and 65 …………………………………….69 6. ROMP of COE With Catalysts 67-69 …………………………………………...72 7. RCM of DEDAM With Catalysts 67-69 ……………………………..…………..73 8. RCM Reactions of DEDAM With Catalysts 12, 70, 77, and 78 ……………...75 9. ROMP Reactions of COE With Catalysts 79-82 ..…………..………………...77 10. RCM Reactions of DEDAM With Catalysts 79-82 ………………..…………...78 11. ROMP Reactions of COE With Catalyst Complex 87 ..……………………….79 12. RCM Reactions of DEDAM With Catalyst Complex 87 ………………………79 13. RCM of 97 With Catalyst 65 ……………………………………………………..88 14. RCM of DAM With Catalysts Bearing ITap Ligands …………………………..89 15. ROMP of Norbornene Substrate 96 With Catalyst 70 ………………………..91 16. ROMP Reactions of Norbornene Substrate 96 With Catalysts 77 and 78 …92 17. Results for Studies of Ru-Metal Removal After RCM Reactions ……..……..99 18. Gelation Studies of DCPD and COE ………………………………..………...101 vii LIST OF ILLUSTRATIONS Figure 1. Mo-Based (Schrock-Type) Catalyst ………………………….…...….……………..10 2. First Ru-Based Carbene Catalyst 4 ………………………………………….…..…11 3. Improved Ru-Based Catalyst 5 ……………………………………………….……..12 4. 18-Electron Allenylidene Complex 10 ………………………………………………13 5. Catalyst 11 by Herrmann et. al. …………………………………………….……….13 6.
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