Louisiana State University LSU Digital Commons LSU Historical Dissertations and Theses Graduate School 2000 I. New Routes to the Synthesis of Chelating Phosphines for Use in Hydroformylation Catalysis. II. Organometallic Complexes of Convex Hydrocarbons. Barry J. Misquitta Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses Recommended Citation Misquitta, Barry J., "I. New Routes to the Synthesis of Chelating Phosphines for Use in Hydroformylation Catalysis. II. Organometallic Complexes of Convex Hydrocarbons." (2000). LSU Historical Dissertations and Theses. 7213. https://digitalcommons.lsu.edu/gradschool_disstheses/7213 This Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons. It has been accepted for inclusion in LSU Historical Dissertations and Theses by an authorized administrator of LSU Digital Commons. 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ORGANOMETALLIC COMPLEXES OF CONVEX HYDROCARBONS A Dissertation Submitted to the Graduate Faculty of the Louisiana State University and Agricultural and Mechanical College in partial fulfillment of the Requirements for the degree of Doctor of Philosophy in The Department of Chemistry by Barry J. Misquitta B.Sc. University of Bombay, 1989 D.I.A.C. Ramnarian Ruia College, 1990 D.S.M. National Institute of Technology, 1990 M.S. University of North Carolina at Greensboro, 1993 May 2000 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. UMI Number 9979277 UMI' UMI Microform9979277 Copyright 2000 by Bell & Howell Information and Learning Company. All rights reserved. This microform edition is protected against unauthorized copying under Title 17, United States Code. Beil & Howell Information and Learning Company 300 North Zeeb Road P.O. Box 1346 Ann Arbor, Ml 48106-1346 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. The great tragedy of Science - the slaying of a beautiful hypothesis by an ugly fact T. H. Huxley 1825 - 1895 ii Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. ACKNOWLEDGMENTS I would like to thank Dr. George Stanley for his tuition and guidance and especially for his academic and financial support during my graduate studies. Thanks once again for allowing me experimental free reign in the laboratory. And to the future doctor, Petia Gueorgieva, for allowing me to teach her all I know about phosphines and synthetic techniques. I would also like to thank Dean Peter Rabideau for his financial support. Dr. Andrez Sygula and especially Renata Sygula for supplying me with ton quantities of corannulene, thereby ensuring that the latter half of this work could be pursued. That being said, it wouldn’t be fair not to acknowledge the Sygula’s for their support and frequent invitations to dinner. This resulted in the most pleasant company over the best home cooked meals I’ve had this side of the Atlantic. To Dr. Fred Koch and Dr. Bill Glover for showing me that there exists a world outside of chemistry. Thanks for all the weekends spent teaching me everything I know about all things mechanical and especially for fostering my fascination with classic American muscle cars. I will especially miss the Sunday fishing trips that were almost as good as going to church. To my friends, the recent Dr. Charles Cantrell and Dr. Mark Clayton and who, along with their families, welcomed me with their laughter and support during the last five years. It was these two ‘rednecks’ that kindled my love of the hunt. For these boys the sight of me tramping across the woods all over the state of Louisiana dressed in leather, jackbooted and armed with various high caliber rifles resulted in the affectionate title of ‘the anorexic terminator’. iii Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. And to my best friend the fiery Italian, Dr. Maria Giulia Salgo, a big thank you for your company, support and friendship through the years, especially for the alcoholic adventures across this ‘cosmopolitan’ city. Henceforth, the happy haze of the drunken hour provided ample opportunity to set straight my perspectives for the new day. All this of course helped ease my right of passage through graduate school. Thank you. And almost last but not the least, this work is for my parents and family who loved and supported me through the years. Thank you so much for letting me leave the nest and discover the world and allowing me to spend so much time being a student. Thank you also for bending my ear to get this over with, so that I may move on. And for a mischievous spirit ‘Gwenhwyfar’ who has a disconcerting habit of demanding my full attention in sometimes subversive and startling ways. iv Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. TABLE OF CONTENTS EPIGRAPH..............................................................................................................................ii ACKNOWLEDGEMENTS.................................................................................................. iii LIST OF FIGURES............................................................................................................... vii LIST OF SCHEMES............................................................................................................... x ABSTRACT............................................................................................................................xi CHAPTER 1. INTRODUCTION.......................................................................................... 1 1 . 1 . Mechanism for Hydroformylation ...............................................................................2 1.2. Polymetallic Catalysts ...................................................................................................5 CHAPTER 2. HOMOGENEOUS BIMETALLIC HYDROFORMYLATION CATALYSIS.................................................................................................. 7 2.1. Stanley Bimetallic Hydroformylation Catalyst ...........................................................7 2.2. Mechanism and Homobimetallic Cooperativity of Catalyst .................................... 10 2.3. Catalyst Binding S ite ..................................................................................................13 CHAPTER 3. NEW ROUTES FOR LIGAND MODIFICATION.................................... 15 3.1. Synthesis of et,ph-P4 ..................................................................................................15 3.2. Preparative History of Halophosphines (of type RPX 2 and R 2 PX).........................16 3.2.1. From Aromatic Compounds and Phosphorus(III) Halides ................................ 16 3.2.2. From Phosphorus Acid Derivatives .....................................................................18 3.2.3. From Phosphorus Halides and Organometallic Compounds .............................19 3.3. Preparation of Ordinary Organozinc Reagents by Transmetalation ....................... 21 3.4. Experimental ............................................................................................................... 22 3.5. Results and Discussion .............................................................................................. 30 3.5.1. The Methyl Anomaly ........................................................................................... 35 3.5.2. The Use of High Boiling Solvents to Aid Isolation .......................................... 37 3.5.3. Use of Grignard in High Boiling Solvents to Aid in Isolation of Me 2 PCl 37 3.5.4. Use of Dialkylzinc and RLi to Realize the Synthesis of Me 2 PCl....................