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A Dissertation Entitled Synthesis, Reactivity, and Catalysis of 3-Iminophosphine Palladium Complexes by Andrew Ronald Shaffer Submitted as partial fulfillment of the requirements for the Doctor of Philosophy in Chemistry ____________________________________ Advisor: Joseph A. R. Schmidt ____________________________________ Committee Member: Mark R. Mason ____________________________________ Committee Member: Yun-Ming Lin ____________________________________ Committee Member: Brian Ashburner ____________________________________ College of Graduate Studies The University of Toledo August 2009 An Abstract of Synthesis, Reactivity, and Catalysis of 3-Iminophosphine Palladium Complexes by Andrew Ronald Shaffer Submitted as partial fulfillment of the requirements for The Doctor of Philosophy in Chemistry The University of Toledo August 2009 Chapter 1. A brief outline, as well as a time table, of organometallic chemistry is described to better acquaint the reader with the field. Several detailed explanations of catalysis, specifically hydroamination, aryl amination, and Suzuki cross-coupling are presented in a very general context. Finally, basic principles of ligands and their design are outlined, as well as the importance of the research conducted herein. Chapter 2. Twenty-six new α,β-unsaturated β-chloroimines were synthesized from commercially available ketones using the Vilsmeier-Haack reagent, followed by Schiff- base condensation. Each imine was subsequently converted to an α,β-unsaturated 3- iminophosphine through either late-metal catalyzed phosphorus-carbon cross-coupling or via an addition/elimination sequence. Depending on the substituents present on the vinyl ii group, the resultant phosphines were isolated as either E- or Z-diastereomers with successful isolation of predominately single diastereomers for all twenty-seven new phosphines investigated. Chapter 3. Several palladium(II) 3-iminophosphine complexes were synthesized in moderate to high yield. With relevance to many palladium-catalyzed coupling reactions, these complexes incorporated a wide variety of ligands, including amines, alkyls, allyls, and triflates. The presence of both η1- and η2-coordination modes demonstrates the hemilability of the 3-iminophosphine ligand class, as determined by X-ray crystallography and NMR spectroscopy. Chapter 4. Catalytic screening of various palladium(II) 3-iminophosphine complexes led to the generation of a wide array of products. The catalytic systems investigated were hydroamination and several cross-coupling reactions including aryl amination and Suzuki cross-coupling. The final products of the catalyses were monitored by GC for product conversion while being isolated and characterized by standard organic techniques and spectroscopy. iii Dedicated to Patrica and Charles Walker my grandparents and Debra and Joseph Thompson my parents and Melissa Shaffer my wife iv Acknowledgements While you cannot choose who your family is, I was extremely blessed with an outstanding one, and without them, I would not be the person I am today and would not have aspired to ask more of myself. In particular, I would like to thank my mom and my dad for not only unwavering support, but for co-signing quite a few loans to get me through 23 years of school. Together, their advice has been of the highest quality and without their help, I would have quit a long time ago. I am eternally grateful to my gram and pap for always allowing me to have a place to call home. Some of my greatest qualities are a direct result of their teachings and beliefs and I hope that I will be half the inspiration to others as they were to me. I would also like to thank my uncles and their wives for being positive influences on how to live with your soul mate and how to raise incredible children. Finally, I would like to thank my cousins, as well as the rest of my extended family for the laughs, cries, and great stories that I have been fortunate enough to be part of. You do however get to choose who your friends are. Growing up as a lonely child, I looked to my friends as my brothers and sisters and I would without thinking push an innocent bystander in front of a bullet for them. I think it would be best to start with the first friend I had. Jeff Spagnolla and I were probably the hardest working dishwashers Mahaffey ever saw and will see. Those hours would have seemed unending without his companionship. When I changed schools at the beginning of 7th grade, I was fortunate enough to meet my best friend Matt as well as JT, Curt, and Cliff. And while the stories we have shared would probably make a great novel, publishing it would probably get us either subpoenaed or arrested. When I attended UPJ with Curt and Matt, v I had the opportunity to meet several other unique individuals that I am fortunate enough to call friends. At any time, I am sure Aric, Munster, Danimal, Ted, Hartman, Seth, Janet, Jess, Justin, Tyson, Doug, Joe, Dan, Troy, Kelli, and Ashely could tell you their favorite Bad One story. It was only with their help that I was able to remain sane enough to be a chemistry major. The final group of friends is those that I have made at my time at UT. Without the occasional rant, deathmatch, or pickup game, it would have been impossible to be the indentured servant that I needed to be throughout grad school. A special thanks to my first two lab mates who endured the ‘Dark Times’ with me as well as to Matt for the multiple 7-11 days we shared together. And a final thank you for the remaining three, who by joining the lab allowed the boss to let me move on. While my family developed my morals and beliefs, there were a few teachers that inspired me. Mrs. Spencer, my 3rd grade teacher and Mr. Love, my 6th grade teacher, instilled a fire that I rely on even now to motivate me. Their greatest lesson was teaching me never to believe you are worthless and you can succeed no matter what your address is or what side of the bridge you were raised. My love of science started in 10th grade with Mr. Petrunak’s College Prep Biology class mainly because his relentliness to accept average always challenged me. Well, I wouldn’t probably have been a chemist, unless it was for Ms. Mellot’s classes because it was there I found myself and realized that chemistry was my calling. While I could list a whole set of professors who have helped me get through undergraduate and graduate school, I will only list two. Dr. Joseph Carney was the epitamey of what I thought a scientist should be: crazy style, focused, and scatter brained (but only because he was thinking about twenty things at once). Dr. C was not only my undergraduate advisor, but a true inspiration. He was the largest reason vi I thought of becoming an analytical chemist and was always very supportive as well as very understanding. Dr. Joseph Schmidt was about as different from Dr. C as one could get. Joe was hip, young, energetic, and just as brilliant, only more composed. Without his guidance and oversight (he literally looked over my shoulder for the first two years of my graduate life), I would not be half the synthetic chemist I am. His constant encouragement and support inspired me to always demand more out of my skills and for me to learn new ones as well. If certain traits were not driven home as firmly as they were, I would have probably blown myself up, burnt down or flooded the lab, or died from phosphine asphyxiation. The last person I would like to thank is my wife, Melissa. She was not only a source of inspiration but that of comfort. She allowed me to see life outside of lab and has taught me how to care about life, not work. And although we have had our ups and downs, I would not trade a single down for an up with someone else. Your love and support brings peace to my heart and I will spend the rest of my life thanking you for your love, patience and understanding. I love you. vii VITA June 1, 1981 – Born – Clearfield, PA 2004 Bachelor of Science, University of Pittsburgh at Johnstown 2004-2009 Research/Teaching Assistant, The University of Toledo 2009 Doctor of Philosophy, The University of Toledo Publications Shaffer, A. R.; Schmidt, J. A. R. Palladium(II) 3-Iminophosphine Complexes as Intermolecular Hydroamination Catalysts for the Formation of Imines and Enamines. Organometallics 2008, 27, 1259-1266. Shaffer, A. R.; Schmidt, J. A. R.. A Versatile Methodology for the Synthesis of α,β- Unsaturated 3-Iminophosphines. Chemistry-A European Journal 2009, 15, 2662-2673. Shaffer, A. R.; Schmidt, J. A. R. Reactivity of (3-Iminophosphine)Palladium(II) Complexes: Evidence of Hemilability. Organometallics 2009, 28, 2494-2504. viii Table of Contents Abstract................................................................................................................................ii Dedication...........................................................................................................................iv Acknowledgements..............................................................................................................v Vita...................................................................................................................................viii Publications......................................................................................................................viii Table of Contents................................................................................................................ix List of Figures....................................................................................................................xii
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