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Metathesis of Functionalized Alkanes: Understanding the Unsolved Problem

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Metathesis of Functionalized Alkanes: Understanding the Unsolved Problem Metathesis of functionalized alkanes: understanding the unsolved problem Dissertation by Mykyta Tretiakov In Partial Fulfillment of the Requirements For the Degree of Doctor of Philosophy King Abdullah University of Science and Technology Thuwal, Kingdom of Saudi Arabia October, 2019 EXAMINATION COMMITTEE PAGE The dissertation of Mykyta Tretiakov is approved by the examination committee. Committee Chairperson: Professor Jean-Marie Basset Committee Members: Professor Kuo-Wei Huang, Professor Osman Bakr, Professor Pascal Saikaly, Professor Didier Astruc © October 2019 Mykyta Tretiakov All Rights Reserved ABSTRACT The aim of this dissertation is to discover the metathesis of functionalized alkane. The first chapter describes an overview of the catalysis field, the role of surface organometallic chemistry (SOMC) and the history of metathesis. The second chapter studies the decomposition of the alkane metathesis catalyst precursor based on WMe6 grafted on partially dehydroxylated at 700 °C silica (SiO2-700) [≡Si-O-WMe5] and its activity in the metathesis of non-coordinating substrates. We used thermal programmed desorption (TPD), in situ infrared-mass spectrometry (IRMS) and chemical techniques with nuclear magnetic resonance. We found evidence of decomposition of the catalyst by coordinating substrates (ester and alcohol) and its inactivity in the metathesis of siloxanes and silanes. [≡Si-O-WMe5] catalyzes the disproportionation of n-butyl-ferrocene to ferrocene and dibutylferrocene. The third chapter is dedicated to the strategy of protection of the catalyst active site by modification of the catalyst support. We modified conventional silica which was partially dehydroxylated at 500 °C, and KCC-1 supports by octyltriethoxysilane as well as 1,1,2,2- tetrahydro-perfluorooctyl-triethoxysilane and grafted the alkane metathesis catalyst precursor – W(CH3)6. The obtained materials have been thoroughly characterized and studied in catalysis showing the activity towards metathesis of olefins and alkanes, but were inactive in the metathesis of functionalized alkanes. The fourth chapter provides the strategy with which to design and metathesize a compatible functionalized alkane on well-defined alkane metathesis catalyst. We investigated the weak coordinating pyrrole-based family of substrates. While utilizing [≡Si-O-WMe5] with 1-(alkyl)-2,5- dimethyl-1H-pyrroles, traces of metathesis and isomerization products were observed. With these results, we synthesized a rigid aromatic molecule – 9-hexyl-9H-carbazole and reached 5 % conversion to lower and higher homologs. That result proved to be the first-ever known example of metathesis of a functionalized alkane. The fifth chapter details the strategy of utilizing the bimetallic catalysts based on supported late (Ir and Ru) and early (W and Ti) transition metal complexes, as well as a combination of late and early (Ru and Ti). All the systems were thoroughly characterized by FTIR and SS-NMR techniques and showed remarkable activity in the metathesis of alkanes. The sixth chapter provides conclusions and future outlook. ACKNOWLEDGMENTS I would like to sincerely thank everyone who contributed to the work presented in this dissertation. Exceptional thanks go to my supervisor, Professor Jean-Marie Basset. I am extremely honored to be his Ph.D. student and to work in his lab. My Ph.D. has been a very challenging and fantastic experience, and I thank Professor Basset not only for his tremendous academic support but also for giving me so many excellent opportunities to learn and to grow professionally. I thank him for the most challenging research project of my entire chemistry career and for the freedom he gave me to fight against the challenges. I thank him for his guidance and for our long discussions which sparked lots of new ideas and bright thoughts. I will forever remember these moments. Most enormous gratitude goes to Dr. Manoja Samantaray, who taught me many techniques of surface organometallic chemistry, fruitfully discussed results, improved my scientific writing skills, and taught me to stay motivated during very challenging periods. Special thanks go to my committee members Professor Kuo-Wei Huang, Professor Osman Bakr, Professor Pascal Saikaly, and Professor Didier Astruc. I want to thank many other people who significantly contributed to my work, Dr. Yury Lebedev for his excellent contribution to our work with ferrocenes, silicon compounds and metathesis of carbazole, Dr. Hicham Idriss and Dr. Shahid Bashir from SABIC for giving me an opportunity to work on an in-situ IR MS instrument and significant intellectual contribution to the work, Prof. Valentin Rodionov for collaboration in metathesis catalysts on modified hydrophobic supports, Aya Saidi for our collaboration in hydro-metathesis projects and WMe6 preparations, Dr. Sanjay Lolage for his contribution and help with preparation of bimetallic metathesis-dehydrogenation catalysts, and Dr. Youssef Saih and Dr. Jullian Vittenet for their wonderful training on dynamic flow PID reactors. I thank Dr. Abdelhamid Emwas and Dr. Edy Abou-Hamad for their contribution in many solid-state NMR experiments, and Dr. Anissa Bendjeriou Sedjerari for her guidance and discussions of silica synthesis, Dr. Sergei Lopatin for TEM characterizations and KAUST Core Lab. Finally, exceptional thanks goes to my wife Elena, and my parents Alina and Sergii for their support and patience while I was doing my Ph.D. Table of Contents EXAMINATION COMMITTEE PAGE .................................................................................................. 2 ABSTRACT ....................................................................................................................................... 4 ACKNOWLEDGMENTS .................................................................................................................... 6 Table of Contents ........................................................................................................................... 8 LIST OF ABBREVIATIONS ............................................................................................................... 15 LIST OF FIGURES ............................................................................................................................ 18 LIST OF SCHEMES .......................................................................................................................... 26 LIST OF TABLES .............................................................................................................................. 29 Chapter 1: Bibliography ............................................................................................................... 30 1. Introduction .......................................................................................................................... 31 1.1. Introduction to catalysis ................................................................................................... 31 1.1.1 Homogeneous catalysis ................................................................................................... 32 1.1.2 Heterogeneous catalysis ................................................................................................. 33 1.1.3 Advantages and disadvantages of homogeneous and heterogeneous catalysis ......... 34 1.1.4 Surface organometallic chemistry (SOMC) – combining advantages of homogeneous and heterogeneous catalysis .................................................................................................... 35 1.2. Catalyst Supports .............................................................................................................. 36 1.2.1 Silica ................................................................................................................................. 37 1.2.2 Alumina ............................................................................................................................ 39 1.2.3 Silica-alumina ................................................................................................................... 41 1.2.4 Other supports ................................................................................................................. 42 1.3. Grafting of metal complexes ............................................................................................ 43 1.4. Single-site approach .......................................................................................................... 45 1.5. Surface organometallic fragments (SOMF) ...................................................................... 46 1.6. The predictive approach of heterogeneous catalysis and catalysis by design ............... 47 1.7. Application of SOMC in catalysis ...................................................................................... 49 1.7.1 Olefin metathesis ............................................................................................................ 49 1.7.2 Alkane metathesis ........................................................................................................... 50 1.7.3 Olefin hydro-metathesis ................................................................................................. 52 1.7.4 Imine metathesis ............................................................................................................. 53 1.7.5 Polymerization ................................................................................................................. 54 1.7.6 Alkyne
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