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(Title of the Thesis)* FLUOROCARBENE, FLUOROALKYL, AND FLUORIDE COMPLEXES OF FIRST-ROW TRANSITION METALS Graham Mark Lee Thesis submitted to the Faculty of Graduate and Postdoctoral Studies University of Ottawa In partial fulfillment of the requirements for the degree of Doctor of Philosophy Ottawa-Carleton Chemistry Institute Faculty of Science University of Ottawa © Graham Mark Lee, Ottawa, Canada, 2017 Abstract Fluorinated organic compounds play important roles in our society, as these products range from life-saving pharmaceuticals and agrochemicals, to fluoropolymers with extremely high thermal and chemical stability. Although elemental fluorine (F2) is the most reactive element, some fluoro- organic compounds are chemically inert. As such, controlled reactivity of fluorine or highly- fluorinated organic fragments is a considerable, yet important challenge for synthetic chemists. Fluoro-organometallic chemistry has been studied for decades, as researchers attempt to maximize the potential of metal mediated/catalyzed processes for the synthesis of fluorinated organic molecules. Within this framework, metal fluorocarbene complexes are particularly interesting because of their highly tunable reactivity, and are proposed for use in important metathesis/polymerization reactions of perfluorinated alkenes. While considerable work is still needed to make these proposed reactions a reality, this thesis outlines contributions from our F F research group. We showed that cobalt fluorocarbene complexes CpCo(=CFR )(PPh2Me) (R = F, CF3) undergo [2+2] cycloaddition reactions with tetrafluoroethylene (TFE) and phenylacetylene to form perfluorometallacyclobutane and partially fluorinated metallacyclobutene products, respectively. For both reactions, computational studies reveal a stepwise ring-closing mechanism, which proceeds through a singlet 1,4-diradical intermediate. Next, the formation of CpCo(=CF2)(L) complexes is achieved via the direct addition of difluorocarbene, generated in situ, to a cobalt(I) precursor. Subsequent addition of CF2 to cobalt fluorocarbene complexes results in [2+1] cycloaddition and formation of perfluorinated alkene complexes. The [2+1] addition is highly favored as the cobalt fluorocarbenes readily react with ii electrophilic CF2. A series of experiments provide evidence for the stepwise nature of fluoroalkene complex formation. From Co(I) fluorocarbene complexes, the focus shifts to preparing metal fluorocarbenes with electrophilic-type reactivity. The synthesis of bis(perfluoroalkyl) complexes serve as precursors for preparation of perfluoroalkyl cobalt(III) fluorocarbenes, which undergo migratory insertion reactions of the fluorocarbene into the perfluoroalkyl ligand. Using a similar synthetic approach, nickel(II) and palladium(II) difluorocarbene complexes are prepared from their corresponding trifluoromethyl precursors. The synthesis, characterization and reactivity of cobalt(III) fluoride complexes is also described, including the catalytic fluorination of acyl chlorides, demonstrating the first example of a cobalt(III) catalyzed fluorination reaction. The effects of the various ancillary ligands on these cobalt catalysts are investigated using high-throughput experimentation technology, and the scope of the reaction is expanded to include the synthesis of a variety of acyl fluoride compounds. Finally, the results and learnings from this work will be summarized and highlighted. The future directions and novel research which could result from the continuation of these projects is discussed, with an emphasis placed on the areas believed to have the highest potential impact. iii Acknowledgements My Ph.D. work was made possible by my supervisor, Professor Tom Baker. Thank you for being an excellent mentor over the years, and for making grad school such a fun experience. You always made time for me, and gave me so many incredible opportunities which have changed my life for the better. I can’t thank you enough, it’s been a privilege to be a part of your research group, and I had a blast! To Dan Harrison, thank you for being a great friend and an incredible chemist. The work in this thesis was inspired to a great extent by conversations with you, and I appreciate your guidance and mentorship a tremendous amount. To all the current and former members of the Baker research group, Christian, Kaitie, Matt, Alex, Nick, Uttam, Mehdi, it was a pleasure to work with all of you, and your friendship means so much. Thank you to the incredible staff at the University of Ottawa, who helped make this work possible, Ilia Korobkov, Serge Gorelsky, Glenn Facey, Eric Ye, and Roxanne Clément. To my undergraduate supervisor, Professor Steve Westcott. Thanks for getting me this far, and for all the support and encouragement over the years. To my international supervisors, Professor Elena Fernandez and Dr. Don Bierer, thank you for the wonderful opportunity to work in your labs. Thanks to all of my family and friends, I love you all so much. Mom and Dad, thanks for always supporting me, I couldn’t have done it without you. Holly and Cole, thank you both for believing in me and supporting me. To Dave, Dan, Hamza and Nick, thanks for all the fun times. To my beautiful wife Arianna, your love and support means everything to me. iv Table of Contents Abstract ............................................................................................................................................ ii Acknowledgements ......................................................................................................................... iv List of Figures ................................................................................................................................. ix List of Schemes .............................................................................................................................. xii List of Tables ................................................................................................................................ xiv Abbreviations ................................................................................................................................. xv Chapter 1 .......................................................................................................................................... 1 1.1 Published Contributions ......................................................................................................... 1 1.2 Fluorine in Organometallic Chemistry: Context for Research .............................................. 1 1.2.1 Impetus for Studying Fluoro-Organometallic Chemistry ............................................... 1 1.2.2 Overview of Fluoro-Organometallic Complexes ............................................................ 2 1.3 Metal Fluoroalkyl Complexes ................................................................................................ 4 1.3.1 Synthesis of Metal Fluoroalkyls ..................................................................................... 4 1.3.2 Reactivity of Metal Fluoroalkyl Complexes ................................................................... 8 1.4 Metal Fluorocarbene Complexes ........................................................................................... 8 1.4.1 Overview of Metal Fluorocarbenes ................................................................................. 8 1.4.2 Bonding in Metal Fluorocarbenes ................................................................................. 10 1.4.3 Synthesis and Characterization of Metal Fluorocarbenes ............................................. 12 1.4.4 Reactivity of Metal Fluorocarbenes .............................................................................. 18 1.5 Organometallic Fluoride Complexes ................................................................................... 24 1.5.1 Synthesis and Characterization ..................................................................................... 25 1.5.2 Metal Catalyzed Nucleophilic Fluorination .................................................................. 26 1.6 Summary and Thesis Outline ............................................................................................... 28 1.7 References ............................................................................................................................ 29 Chapter 2 ........................................................................................................................................ 33 2.1 Context and Objectives ........................................................................................................ 33 2.1.1 Published Contributions ................................................................................................ 34 2.2 Experimental and Computational Evidence for 1,4-Diradical Intermediates in Reactions of Cobalt Fluorocarbene Complexes with Terminal Aryl-alkynes to give Metallacyclobutenes .. 35 2.2.1 Introduction ................................................................................................................... 35 v 2.2.2 Results and Discussion ................................................................................................. 37 2.2.3 Conclusions ................................................................................................................... 50 2.3 Experimental Details for Section 2.2 ................................................................................... 50 2.3.1 General Information
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