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New Organosilicon Chemistry Paulina Elena Gonzalez Navarro University of Texas at El Paso, [email protected]

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New Organosilicon Chemistry Paulina Elena Gonzalez Navarro University of Texas at El Paso, Paulinaegonzalez@Live.Com University of Texas at El Paso DigitalCommons@UTEP Open Access Theses & Dissertations 2016-01-01 New Organosilicon Chemistry Paulina Elena Gonzalez Navarro University of Texas at El Paso, [email protected] Follow this and additional works at: https://digitalcommons.utep.edu/open_etd Part of the Chemistry Commons Recommended Citation Gonzalez Navarro, Paulina Elena, "New Organosilicon Chemistry" (2016). Open Access Theses & Dissertations. 654. https://digitalcommons.utep.edu/open_etd/654 This is brought to you for free and open access by DigitalCommons@UTEP. It has been accepted for inclusion in Open Access Theses & Dissertations by an authorized administrator of DigitalCommons@UTEP. For more information, please contact [email protected]. NEW ORGANOSILICON CHEMISTRY PAULINA ELENA GONZALEZ NAVARRO Doctoral Program in Chemistry APPROVED: Keith H. Pannell, Ph.D., Chair Hemant K. Sharma, Ph.D. Rosa Maldonado, Ph.D. Shizue Mito, Ph.D. Skye Fortier, Ph.D. Charles Ambler, Ph.D. Dean of the Graduate School Copyright © by Paulina Elena Gonzalez Navarro 2016 DEDICATION Este trabajo está dedicado a mi Familia, especialmente a mi Papá, Pepe González, quien me motivó a llegar más lejos, a tener una mayor preparación profesional, a crecer como persona, y a luchar por mis metas. A pesar de que se fue al cielo cuando yo apenas empezaba el doctorado, seguí de pie tratando de corresponder con todo lo que él en vida hizo por mí. A mi Mamá, Ma. Elena Navarro, una mujer hermosa y fuerte, quien es el pilar de la familia y que da todo por sus hijos, que gracias a su amor y el de mis hermanos, me hicieron seguir adelante. A José y Alejandra, mis hermanos, quienes siempre me han apoyado sin importar las circunstancias y por ser los amigos incondicionales. A mi esposo Ricardo, mi compañero de vida, que, gracias a su amor, apoyo y paciencia, este camino se hizo más ligero y placentero. NEW ORGANOSILICON CHEMISTRY by PAULINA ELENA GONZALEZ NAVARRO, B.Sc. in Chemistry DISSERTATION Presented to the Faculty of the Graduate School of The University of Texas at El Paso in Partial Fulfillment of the Requirements for the Degree of DOCTOR OF PHILOSOPHY Department of Chemistry THE UNIVERSITY OF TEXAS AT EL PASO December 2016 ACKNOWLEDGEMENTS I would like to express my sincere gratitude to my advisor, Dr. Keith H. Pannell, for his expert guidance, constant encouragement, wise knowledge, and motivational enthusiasm shown throughout the course of these years. He is the best mentor that I could have, a great friend and amazing person. I am very thankful he gave me the opportunity to work in his research group, for helping me become a better scientist, and for his support when I most needed it. To Dr. Hemant Sharma, who showed me many laboratory techniques, how to do research and the valuable insights and recommendations. He has been a good friend, always helping me with my projects and for pushing me to improve my skills. I would like to acknowledge my committee members Professors Dr. Shizue Mito, Dr. Skye Fortier, and Dr. Rosa Maldonado for the time and help they spent during the achievement of this dissertation. I also want to thank Dr. Alejandro Metta-Magaña for his assistance in solving X-ray crystal structures of compounds herein presented. Special thanks to Dr. Dale Alexander, who accepted me as his Teacher Assistant in the Periodic Table Laboratory. It was the greatest teaching experience that I could have. He is the best Professor that a student could hope, with his sense of humor, simple experiments and explanations, learning and teaching chemistry was so much fun. I thank my lab mates Isabel Saucedo, Dr. Renzo Arias, Dr. Robinson Roacho, Dr. Sanchita Chakrabarty, Alexander Craig, Jorge Martinez, and Raul Cuevas for the science discussions, collaborations, good moments, laughs and all the fun we shared together during these years, and all the students that have done research in Dr. Pannell’s laboratory: Peiyu, Yangjie, Lianqian, Sarah, Alex, Joe, Liz, Matt and David. In addition, I like to thank the faculty and staff from the UTEP Chemistry Department, especially to Dr. Katja Michael and Dr. Mahesh Narayan, for their guidance and help during my doctoral studies. The research was supported by the Robert Welch Foundation, Houston, Texas. v I gratefully acknowledge my family for all support and unconditional love. Thank you mom and dad for educating me and making me the person that I am now. To my siblings, José and Alejandra, for your support and cheerfulness. To María Jose, the new family member, for bringing happiness in the family. To my husband, Ricardo Perez, for his patience, help and love, for making me laugh even when I was extremely stressed. To my friends, my favorite people, Lizeth Rivera, Griselda Lopez and Lineth Rivera, for being more than friends, thank you for all the sleepless nights, great and bad moments, adventures, for taking care of me when I most needed it, and most importantly for being my family in Texas and allowing me to feel at home. To Marisol Romero, Dr. Danisha Rivera, Dr. Roberto de la Torre, Ana Melendez, and the Gaias soccer team: Iliana, Andrea, Kari, Karen, Galia, and Nalle, for the friendship and all the memorable experiences we have been through. I also thank my grandmas, aunties, uncles and cousins for their support. Finally, I thank God for blessing me with the most wonderful family, husband, and friends, for the great opportunities and for helping me to achieve the goals in my life. Without all of you, your help and support, this work would never have been possible, THANK YOU! vi ABSTRACT The formation of siloxymethylamine intermediates R3SiOCH2NMe2, 1, as initial products of the reduction of DMF by hydrosilanes catalyzed by Mo(CO)5NMe3 has been reported. These siloxymethylamines can react with R’3SiH to form trimethylamine and disiloxanes, and with chlorosilanes to form disiloxanes and ClCH2NMe2, Eschenmoser’s salt. I shall illustrate, in Chapter 1, how attempts to react 1, formed in situ in the presence of chlorosilanes R’3SiCl in the hope producing heterosilyl disiloxanes, R3SiOSiR’3, was not successful but led to a newly discovered activation of the Si-Cl bond by DMF. - In Chapter 2, we surmised that 1 acts as a transient siloxy-imminium ion pair [R3SiO] + [CH2NMe2] , and further suggested that these intermediates could be useful Mannich reagents, dimethylaminomethyl [Me2NCH2] transfer agents. Furthermore, I shall present the reactions between 1 and compounds with a series of E-H bonds (E = O, S, N) which prove its utility and reliability as a new [CH2NMe2] transfer reagent. We have previously reported the formation of a series of group 14 substituted methanes, (R3E)nCH4-n (E = Si, Ge, Sn, Pb; R = combinations of methyl and aryl groups; n = 2,3,4). We also used these materials where an R group = C6H5 to form Cr(CO)3 derivatives. During such studies we observed significant C-E bond cleavage products to form (R3E)n-1CH4-n products. It was proposed that the Cr(CO)3 substituent was responsible for this E-C bond activation. Now we have synthesized silicon and germanium homologous compounds with their Cr(CO)3 derivatives, and will study their hydrolytic stability, Chapter 3. Treatment of arenechromiumtricarbonyl complexes with regular n-Bu2O/THF will also be described to illustrate the potential activation of E-C bonds by the transition metal substituent. vii TABLE OF CONTENTS DEDICATION ...............................................................................................................................III ACKNOWLEDGEMENTS ............................................................................................................ V ABSTRACT ................................................................................................................................. VII TABLE OF CONTENTS ............................................................................................................ VIII LIST OF TABLES ........................................................................................................................ XI LIST OF FIGURES .................................................................................................................... XIII LIST OF SCHEMES................................................................................................................ XVIII CHAPTER 1. ACTIVATION OF CHLOROSILANES BY DMF .................................................1 1.1 Abstract ...................................................................................................................................1 1.2 Research Objectives ................................................................................................................2 1.3 Introduction .............................................................................................................................2 1.3.1 Organometallic Chemistry .............................................................................................2 1.3.2 Organosilanes .................................................................................................................2 1.3.3 Hydrosilanes ..................................................................................................................3 1.3.4 Reduction of Amides to Amines ....................................................................................4 1.3.5 Siloxanes ........................................................................................................................6 1.4 Results and Discussion ...........................................................................................................7
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