Processes at the Interfaces of Electro- and Organic Chemistries by Anuska Shrestha A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy (Chemistry) in the University of Michigan 2020 Doctoral Committee: Professor Melanie S. Sanford, Chair Professor Adam J. Matzger Assistant Professor Charles C. L. McCrory Professor Johannes Schwank Anuska Shrestha [email protected] ORCID iD: 0000-0002-3880-3736 © Anuska Shrestha 2020 For my family ii Acknowledgements It is strange to be defending my thesis in a time when the world is suffering from a pandemic. But this situation stands as an example of my fortune to have a graduate mentor like Melanie. You have always watched out for your students’ health and well- being. Thank you for giving me an opportunity to work in your lab, under your mentorship. You let me work on projects that I had no background on and gave me the time and resources to learn and grow as a chemist. This is the most valuable lesson that I take away from graduate school. I will miss your enthusiasm and energy, that is so infectious, and helped lift me up when I struggled in lab. I want to thank Professor Adam Matzger for all your valuable teachings and mentorships. I got to explore a completely new area of chemistry in your lab during my rotation. You were patient with me through failed MOF syntheses and several MOF characterizations lessons. Your feedbacks and advices were crucial for a successful Karle Symposium (2018). I also want to thank Professor Charles McCrory for your valuable feedback on my work during my candidacy and data meeting. Those conversations helped shape some of the projects that we were working on and we are grateful for the valuable discussions. Professor Matzger, McCrory and Schwank, thank you for serving in my committee and for your valuable feedback during my time in graduate school. A big shout out to my undergraduate mentor, Professor Emily McLaughlin. You have always been there when I needed someone to talk and make (what I thought were) life-changing decisions. I am so proud to be one of your students. You have worked effortlessly to improve college experience of a student like me, and I will always be grateful for your support throughout my career. I also had an opportunity to be a part of JCESR and specifically the redoxmers sub-thrust. The biweekly meetings gave us a platform to share our research and gain iii valuable insights from researchers with different backgrounds and perspective. This was also a great opportunity for a graduate student like me to learn and grow as a scientist. I want to specifically thank our collaborators Professor Matthew S. Sigman and Professor Shelley D. Minteer at the University of Utah for all your help during my graduate school. Thank you for taking your time to address my questions. Zayn Rhodes at the University of Utah, it was great to share our knowledge of flow batteries with you and in turn learn a lot from you as well. I also want to thank the batteries/echem subgroup for the interesting discussions and suggestions when the data did not make sense, or when the experiments did not work as intended. Graduate school would have been a lot harder without mentorship of amazing mentors and colleagues throughout. Firstly, thank you Pablo, my first mentor in graduate school. I learnt a lot about synthesis and organic chemistry from you. You were a great mentor and friend, despite your poor choice in sports team. I want to give a huge shout out to Koen. My PhD would not have been the same without your guidance and mentorship. I learnt so much about redox flow batteries and electrochemistry from you and continue to do so. Whenever I have any questions, I know I can always turn to you. Thank you for answering all my frantic WhatsApp messages. Christo, thank you for the helpful discussions and teaching me about electrochemistry as well. I want to thank all the graduate students and post-docs that I interacted with during my time in the Sanford group. I have learnt so much from each and every one of you. I also made great and life-long friends in the Sanford group. I got really fortunate that I got Katarina as my cubby-mate in my first few years. You helped me boost my confidence when I was a young and a timid graduate student, helped me with all the small things that stressed me out, listened to me complain and found a way to make me feel better. Kuam, I don’t even know where to begin thanking you. You have seen me cry and you have seen me rant. But you have put up with it all and I will be forever grateful to your friendship. Yiyang and Scott, thank you for putting up with me and making sure I was never short of wine in my life. I have highly appreciated your feedback on my work and chemistry and owe much of my success to you guys. Pronay, I have always enjoyed our conversations about (Indian) politics, some stupid cultures back home and other random and ridiculous topics. You have also given me some thoughtful advices, that I’ll always be grateful for. iv Courtney, you been such an inspiration. I have always valued your dedication to uplift women in science. Christian, thank you for all the late-night pep-talks. Melissa, I really enjoyed collaborating with for the C–H functionalization project. Thank you for your continued support even after you graduated. Mark, I could not have asked for anyone better to share the unique experience that my final year graduate school has been. I also want to thank Devin, Liz, Liam, Ellen, and Conor for all the helpful discussions about chemistry and otherwise. Also, thank you Liam and Katarina for letting me play with Obe, Salem and Jasper. During my time in the Sanford group, I also got an opportunity to mentor some amazing graduate students: Ryan and Brianna. I cannot wait to see all the wonderful things that you guys are going to do in your respective careers. Yichao, you always make everyone around you laugh with your crazy impressions and ideas. That made lab a fun place to be. I want to thank my family for their continued support. Mamu and Papa, you have sacrificed so much to get me to where I am today. I am blessed to have you as my parents. I owe all my success to you. Thank you for believing in me, encouraging me to pursue my dreams and letting me fly. Mamu, you are the most amazing person and the best of friend; I aspire to have your level of patience and dedication to family. To all my extended family, thank you for loving me endlessly and motivating me to work harder every day. I have been very fortunate to have emotional support systems outside of lab. Ramesh and India, I have always look forward to our adventures together, and taking the much-needed breaks from lab. Ayousha, Sudeshana, and Shilva, I had never realized I had been missing out on so much fun without girlfriends like you in my life. Thank you for being the emotional support system I didn’t realize I needed. Finally, big shout out to the unsung hero of my graduate school, Bijay. No words are enough to express how grateful I am to you. You have made sure I stayed sane throughout graduate school, oftentimes at the expense of your own sanity. Every time I doubted myself or was low in confidence (which was fairly often), you were there to lift me up. You showed me the world of adventure. I could not have made it through this time without your endless love, support and encouragement. Thank you for always being there for me. v Table of Contents Dedication………………………………………………………………………………………..ii Acknowledgements……………………………………………………………………………..iii List of Figures……………………………………………………………………………………ix List of Schemes…………………………………………………………………………………xv List of Tables…………………………………………………………………………………..xvii List of Abbreviations………………………………………………………………………….xviii Abstract………………………………………………………………………………………….xx Chapter 1: Introduction ................................................................................................. 1 1.1. Synthetic Organic Electrochemistry ............................................................ 1 1.2. Electrocatalysis in C–H Functionalization ................................................... 5 1.3. Redox Flow Batteries ................................................................................. 7 1.4. Organic Molecules in Redox Flow Batteries ............................................... 9 1.5. References ............................................................................................... 15 Chapter 2: Pd-Catalyzed C–H Bond Acetoxylation via Electrochemical Oxidation ................................................................................................................. 20 2.1. Introduction ............................................................................................... 20 2.2. Results and Discussion ............................................................................ 23 2.2.1. Initial Stoichiometric Studies ................................................................................ 23 2.2.2. Translation to Catalytic Transformation ................................................................ 25 2.2.3. Complementary Reactivities ................................................................................ 29 vi 2.3. Conclusion and Outlook ........................................................................... 30 2.4. Experimental Details ................................................................................ 31 2.4.1. Instrumental Information .....................................................................................