Iowa State University Capstones, Theses and Graduate Theses and Dissertations Dissertations 2020 Synthesis and reactivity of transition metal complexes supported by oxazolinyl borato ligands and the functionalization of silica surface Abhranil Biswas Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/etd Recommended Citation Biswas, Abhranil, "Synthesis and reactivity of transition metal complexes supported by oxazolinyl borato ligands and the functionalization of silica surface" (2020). Graduate Theses and Dissertations. 17825. https://lib.dr.iastate.edu/etd/17825 This Thesis is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Graduate Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. Synthesis and reactivity of transition metal complexes supported by oxazolinyl borato ligands and the functionalization of silica surface by Abhranil Biswas A dissertation submitted to the graduate faculty in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Major: Organic Chemistry Program of Study Committee: Aaron D Sadow, Major Professor Marek Pruski Igor I. Slowing Levi M. Stanley Wenyu Huang The student author, whose presentation of the scholarship herein was approved by the program of study committee, is solely responsible for the content of this dissertation. The Graduate College will ensure this dissertation is globally accessible and will not permit alterations after a degree is conferred. Iowa State University Ames, Iowa 2020 Copyright © Abhranil Biswas, 2020. All rights reserved. ii DEDICATION To my family and friends iii TABLE OF CONTENTS Page DEDICATION ................................................................................................................................ ii TABLE OF CONTENTS ............................................................................................................... iii ACKNOWLEDGMENTS ...............................................................................................................v ABSTRACT .................................................................................................................................. vii CHAPTER 1. INTRODUCTION ....................................................................................................1 General Introduction .................................................................................................................. 1 Thesis organization .................................................................................................................... 6 References ................................................................................................................................. 7 CHAPTER 2. CO DISPLACEMENT IN AN OXIDATIVE ADDITION OF PRIMARY SILANES TO RHODIUM(I) .........................................................................................................10 Abstract .................................................................................................................................... 10 Introduction ............................................................................................................................. 11 Results and Discussion ............................................................................................................ 15 Conclusion ............................................................................................................................... 26 Experimental Section ............................................................................................................... 30 References ............................................................................................................................... 36 Additional Information ............................................................................................................ 43 CHAPTER 3. SILICA SURFACE MODIFICATION VIA A RU CATALYZED DEHYDROCOUPLING REACTION WITH SILANES ..............................................................50 Abstract .................................................................................................................................... 50 Introduction ............................................................................................................................. 50 Results and discussions ........................................................................................................... 52 Conclusion ............................................................................................................................... 64 Experimental Procedures ......................................................................................................... 65 References ............................................................................................................................... 68 Additional information ............................................................................................................ 73 CHAPTER 4. SYNTHESIS OF A NEW TRIS(OXAZOLINYL)BORATO RUTHENIUM COMPOUND AND ITS APPLICATION IN CATALYTIC CYCLOISOMERIZATION OF 1,6-DIENES ...................................................................................................................................81 Abstract .................................................................................................................................... 81 Introduction ............................................................................................................................. 81 Results and Discussion ............................................................................................................ 83 Conclusions ............................................................................................................................. 91 Experimental Procedures ......................................................................................................... 92 Additional Information .......................................................................................................... 100 References ............................................................................................................................. 104 iv CHAPTER 5. CONCLUSION ....................................................................................................109 General conclusion ........................................................................................................... 109 v ACKNOWLEDGMENTS I deeply appreciate many individuals who have supported and continually encouraged me throughout my Ph.D. life at Iowa State University. Without their time, attention, encouragement, and patience, I would not have been able to see it through. First, I would like to thank my advisor, Prof. Aaron D. Sadow, for giving me an opportunity to work in his research group under his guidance, with suggestions throughout all my years of graduate school. You have set an example of excellence as a researcher, mentor, instructor and role model. I am also very grateful to Aaron for his scientific advice, knowledge and many insightful discussions and suggestions. His guidance helped me in all the time of research and writing this thesis. I could not have imagined having a better advisor and mentor for my Ph.D. study. Besides my advisor, I would like to thank all of my POS committee members Prof. Marek Pruski, Prof. Igor Slowing, Prof. Keith Woo, Prof. Levi Stanley, and Prof. Wenyu Huang for their valuable support, advice and time. I would also like to thank my past and present group members in the Sadow group: Especially, I am grateful to Songchen for training me to use glovebox and Regina for teaching me how to use the Schlenk line and for her assistance in helping perform my first and successful reaction in the Sadow Group. My fellow travelers, Smita and Kasuni who have been on this journey with me and provided much needed encouragement and support. I thank undergraduate student Jacob Brunton, who had conducted research with me in Sadow lab. vi I would like to thank Dr. Igor I. Slowing and the Slowing group members for our collaboration for the synthesis of functionalized silica material. Thanks to Dr. Takeshi Kobayashi and Dr. Zhuoran Wang for their valuable time spent collecting solid-state NMR data for my samples for our collaboration project. I also thank Prof. Marek Pruski for our collaboration. I thank all the chemical instrument services, glass shop, Chemistry Stores and machine shop in the chemistry department. Thanks to Dr. Shu Xu and Dr. Sarah Cady for helping me with several NMR experiments for my research. I would like to thank the Ames Laboratory and Iowa State University for funding and support of my research. I’d also like to thank my Ames family who have been there for me during my ups and downs. I’d like to thank Naresh, Abhishek, Raghu, Aleem, Avipsa, Kalyan, Subhrajit, Judhajit and Saheli for their friendships that helped me immensely in this journey. Special thanks to Ishani for her support and help over that last to two years. It would have been impossible to survive without you. Lastly, I’d like to thank my family (Maa, Baba and brother, Mriganka) for their enormous support and encouragement throughout my life and my graduate school journey. It would