Studies of CH Activation in Unsaturated Amides and Esters by Trinuclear Metal Carbonyl Clusters of Osmium

University of South Carolina Scholar Commons Theses and Dissertations Fall 2019 Studies of CH Activation in Unsaturated Amides and Esters by Trinuclear Metal Carbonyl Clusters of Osmium Morteza Maleki Follow this and additional works at: https://scholarcommons.sc.edu/etd Part of the Chemistry Commons Recommended Citation Maleki, M.(2019). Studies of CH Activation in Unsaturated Amides and Esters by Trinuclear Metal Carbonyl Clusters of Osmium. (Master's thesis). Retrieved from https://scholarcommons.sc.edu/etd/ 5534 This Open Access Thesis is brought to you by Scholar Commons. It has been accepted for inclusion in Theses and Dissertations by an authorized administrator of Scholar Commons. For more information, please contact [email protected]. STUDIES OF CH ACTIVATION IN UNSATURATED AMIDES AND ESTERS BY TRINUCLEAR METAL CARBONYL CLUSTERS OF OSMIUM By Morteza Maleki Bachelor of Science University of Tehran, 2014 Submitted in Partial Fulfillment of the Requirements For the Degree of Master of Science in Chemistry College of Arts and Sciences University of South Carolina 2019 Accepted by: Richard D. Adams, Director of Thesis Aaron K. Vannucci, Reader Cheryl L. Addy, Vice Provost and Dean of the Graduate School © Copyright by Morteza Maleki, 2019 All rights reserved. ii DEDICATION To God, my creator and my savior: The one and only who created me, guided me, and taught me. The one whom I rely on and to whom I shall return. To My Parents, Amir and Masoumeh: The most beautiful people in the world, who sacrificed their lives, so I can go to school and become educated, and will always be proud of me. To my sister, Mahsa: Who has been the most kind and the most compassionate in the tough times. To my love, Sahar: Who has been with me through all the good and tough days, challenges and celebrations. iii ACKNOWLEDGEMENTS I want to appreciate all the help and kindness from Professor Richard D. Adams since when I was his student in CHEM 711. He taught me the basics of cluster and organometallic chemistry, he taught me how to be a good chemist and the most important of all, how to be a good person. This work would not have been possible without guidance, encouragement, and patience from him. I want to thank all my advisory committee members Dr. Aaron Vannucci, Dr. Thomas Makris, and Dr. Esmaiel Jabbari whose suggestions and support made the path much easier for me to progress in my research. I would like to thank Jennifer Merkel, whose unique kindness and sense of responsibility facilitated my admission to the University of South Carolina, and later on, comforted my pursuit of knowledge in the program. I want to thank Dr. Thomas Bryson whose advice and support made the graduate school much less stressful and more pleasant. I want to thank Dr. Amelia Taylor Perry and Dr. Leslie Lovelace who made me a good teacher and taught me how to teach and learn at the same time. I want to thank Dr. Mark Smith whose quick analysis of crystal structures made the progress of our work much faster. Last but not least, I want to thank all the help, support and kindness from all the group members in Dr. Adams’ group: Gaya Elpitiya, Joseph Kiprotich, Jonathan Tedder, Poonam Dhull, Humaiara Akter, Nutan Wakdikar and Meenal Kaushal. Special thanks to Wilson Carter Edenfield for all his work and assistance on this project. iv ABSTRACT The chemistry of the reaction of Os3(CO)10(NCCH3)2 with representatives of unsaturated amides and esters, RCOCHCH2 (R=(CH3)2N, CH3O) has been investigated. In these reactions, it has been observed that a CH bond on the β-carbon atom is readily activated by triosmium carbonyl clusters. The activation of β-carbon C-H bond in unsaturated amides and esters provides a robust platform for studying multicenter C-H bond transformations and for C-C bond formation via hydrogen shift and CO insertion processes. In this work, proposed mechanistic approaches have been taken in order to better understand and study the relationship between the characterized species. In addition, a few non-identified species have been predicted to exist. Furthermore, recommendations on how this work can be further studied and improved have been made. A series of activated unsaturated amides and esters: Os2(CO)6(µ-H)(µ-O=C(N(CH3)2)CHCH), 1, Os4(CO)12(µ- O=C(N(CH3)2)CHCH)2, 2, Os3(CO)9(µ-O=C(N(CH3)2)CH2CHCCHC(N(CH3)2)=O), 3, Os3(CO)8(µ-O=C(N(CH3)2)CHCH)2, 4, Os6(CO)20(µ-H)(µ-O=C(N(CH3)2) CHCH), 5, HOs3(CO)10(µ-O=C(N(CH3)2)CHCH), 6, Os5(CO)15(µ-O=C(N(CH3)2)CHCH)2, 7, and Os3(CO)9(µ-H)(µ-O=C(OCH3)CHCH), 8, were synthesized and isolated. They are described in Chapter 1. Each of the new compounds has been characterized by FT-IR, NMR (1H), mass-spectra and single crystal X-ray diffraction analysis. v TABLE OF CONTENTS DEDICATION ....................................................................................................................... iii ACKNOWLEDGEMENTS ........................................................................................................ iv ABSTRACT ............................................................................................................................v LIST OF FIGURES ................................................................................................................ vii LIST OF SCHEMES .............................................................................................................. viii LIST OF TABLES .................................................................................................................. ix CHAPTER 1 STUDIES OF CH ACTIVATION IN UNSATURATED AMIDES AND ESTERS BY TRINUCLEAR METAL CARBONYL CLUSTERS OF OSMIUM: STUDY, SYNTHESIS AND CHARACTERIZATION .............................................................................................................1 1.1 INTRODUCTION ......................................................................................................1 1.2 EXPERIMENTAL DETAILS .......................................................................................8 1.3 CRYSTALLOGRAPHIC ANALYSES .........................................................................12 1.4 RESULTS AND DISCUSSION ..................................................................................13 1.5 SUMMARY AND CONCLUSIONS ............................................................................32 1.6 REFERENCES ........................................................................................................38 vi LIST OF FIGURES Figure 1.1 Molecular structures of MA (left) and DMA (right) ........................................3 Figure 1.2 Nylon 6,6 synthesis pathway from Adipic Acid and Hexamethylene Diamine ................................................................................................................................5 Figure 1.3 Activation of Methyl Acrylate by Ru5(μ5-C)(CO)15 Complex by Adams et al ..........................................................................................................................6 Figure 1.4 Activation of Vinyl Acetate by Re2(CO)8(μ-C6H5)(μ-H) Complex by Adams et al ..........................................................................................................................7 Figure 1.5 Proposed structure of I*, a saturated 48 e species with the formula of Os3(CO)9(µ-H)(µ3-O=C(N(CH3)2)CHCH) ........................................................................17 Figure 1.6 ORTEP diagram of the molecular structure of Os2(CO)6(µ-H)(µ- O=C(N(CH3)2)CHCH), 1, showing 30% thermal ellipsoid probability ............................20 Figure 1.7 ORTEP diagram of the molecular structure of Os4(CO)12(µ-O=C(N(CH3)2) CHCH)2, 2, showing 25% thermal ellipsoid probability ...................................................21 Figure 1.8 ORTEP diagram of the molecular structure of Os3(CO)9(µ-O=C(N(CH3)2) CH2CHCCHC(N(CH3)2)=O), 3, showing 25% thermal ellipsoid probability ...................22 Figure 1.9 ORTEP diagram of the molecular structure of Os3(CO)8(µ-O=C(N(CH3)2) CHCH)2, 4, showing 15% thermal ellipsoid probability ...................................................24 Figure 1.10 An ORTEP diagram of the molecular structure of Os6(CO)20(µ-H)(µ- O=C(N(CH3)2)CHCH), 5, showing 30% thermal ellipsoid probability ...........................25 Figure 1.11 An ORTEP diagram of the molecular structure of HOs3(CO)10(µ- O=C(N(CH3)2)CHCH), 6, showing 20% thermal ellipsoid probabilities .........................26 Figure 1.12 An ORTEP diagram of the molecular structure of Os5(CO)15(µ- O=C(N(CH3)2)CHCH)2, 7, showing 30% thermal ellipsoid probability ..........................27 Figure 1.13 An ORTEP drawing of the molecular structure of Os3(CO)9(µ-H) (µ-O=C(OCH3)CHCH), 8 showing 30% thermal ellipsoid probability ............................31 vii LIST OF SCHEMES Scheme 1.1 Structure of seven activated compounds resulted from reactions of Os3(CO)10 (NCCH3)2 and DMA: 1, 2, 3, 4, 5, 6, and 7 .......................................................................15 Scheme 1.2 A proposed mechanism of C-H activation of DMA by triosmium carbonyl cluster and formation of I* and 6 ........................................................................18 Scheme 1.3 A proposed scheme for transformation of 6 to 1 ............................................27 Scheme 1.4 A proposed scheme for transformation of 6 to 3 ............................................28 Scheme 1.5 A proposed scheme for transformation of 3 to 4 ............................................29 Scheme 1.6 A proposed scheme for transformation

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