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Photolytic Generation of Nitrenium Ions: Kinetic Studies and Polymerization Reactions

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Photolytic Generation of Nitrenium Ions: Kinetic Studies and Polymerization Reactions ABSTRACT Title of Dissertaion: PHOTOLYTIC GENERATION OF NITRENIUM IONS: KINETIC STUDIES AND POLYMERIZATION REACTIONS Andrew Ching-An Kung, Doctor of Philosophy, 2005 Dissertation directed by: Professor Daniel E. Falvey Department of Chemistry and Biochemistry Nitrenium ions are highly reactive transient species that contain a positively charged and dicoordinate nitrogen atom. The nitrogen atom contains only six electrons in its valence shell and thus the nitrogen is electron deficient and bears a positive charge. Nitrenium ions are of interest due to their suspected role in carcinogenesis since amines are known to form covalent bonds to DNA. The synthesis and photolysis of 1-(N- methyl-N-(1-naphthyl)amino)-2,4,6-trimethylpyridinium tetrafluoroborate, by laser flash photolysis, allowed for the direct observation of N-methyl-1-naphthylnitrenium ion as well as measurements of N-methyl-1-naphthylnitrenium ion’s lifetime and trapping rate constants. It was determined that N-methyl-1-naphthylnitrenium ion has an absorption maximum centered around 500 nm and a lifetime of 835 ns. The trapping rate constants with simple nucleophiles, such as chloride, alcohols, and amines, were determined to be on the order of 108 - 109 M-1s-1. These trapping rate constants were compared to other arylnitrenium ion systems to determine what factors contribute to a chemical’s inherent carcinogenicity. The synthesis and photolysis of 1-(N-methyl-N-(2-naphthyl)amino)- 2,4,6-trimethylpyridinium tetrafluoroborate was also performed. Although no transient intermediate was observed, products from photolysis are consistent with arylnitrenium ion products. Nitrenium ions are also of interest due to their possible role in the polymerization of aniline to form polyaniline (PANI). PANI is of interest because of it is an electronically conducting polymer with many commercial aspects and the mechanism of formation has been under dispute for decades. Although it is generally agreed that the initial dimerization step is due to radical cation coupling, the mechanism for aniline polymerization is argued as proceeding through either a radical cation mechanism or via a nitrenium ion mechanism. Synthesis of a photochemical precursors of an aniline dimer 4-(N-anilino)phenyl azide produced what is believed to be a 4-(N- anilino)phenylnitrenium ion which has an absorption maximum centered around 490 nm. Spectroscopic analysis by MALDI-TOF-MS and X-ray photoelectron spectroscopy (XPS), shows that PANI is a photoproduct. The extrapolated data and results from similar systems, supports the hypothesis that polymerization involves a nitrenium ion intermediate. PHOTOLYTIC GENERATION OF NITRENIUM IONS: KINETIC STUDIES AND POLYMERIZATION REACTIONS by Andrew Ching-An Kung Dissertation submitted to the Faculty of the Graduate School of the University of Maryland, College Park in partial fulfillment of the requirements for the degree of Doctor of Philosophy 2005 Advisory Committee: Professor Daniel E. Falvey, Chair Professor Jeffery T. Davis Professor Philip DeShong Professor Lyle Isaacs Professor Anne E. Simon © Copyright by Andrew Ching-An Kung 2005 DEDICATION This work is dedicated to my parents, Dr. Shain-Dow and Helen Kung, for their support ever since I can remember. I would really like to thank my father for teaching me by example, that the only thing greater than the pursuit of knowledge is family. ii ACKNOWLEDGEMENTS First of all, I would like to thank my advisor, Dr. Daniel E. Falvey not only for his guidance and support, but for his belief in me. Mostly, I would like to thank him for taking a chance on a master’s non-thesis student. I would like to express my gratitude to the faculty of this department for all of their direction, especially Dr. Philip DeShong, Dr. Jeffery T. Davis, and Dr. Lyle Isaacs. From every discussion I’ve had with a faculty member, I have always learned a valuable lesson that I will carry with me into the future. I would like to thank the analytical services for their expertise in their respective fields. These special people would include: Drs. Yiu-Fai Lam and Yinde Wang for their aid in acquiring NMR data; Mr. Noel Whittaker for his skill in mass spectral analysis; and Dr. Bindhu Varughese for her talent in XPS analysis. I would also like to thank Dr. Z. Serpil Gönen-Williams for her help in acquiring XRD patterns, as well as teaching me how to use hooks and needles. I also want to thank my fellow Falvey group members, both past and present. These people include Dr. Sean McIlroy for his guidance during my first years and my fellow Falvey batch mates, Dr. Chitra Sundararajan and Ms. Selina Thomas, for the good times we’ve had over the past five years. I would like to thank the new Falvey kids for keeping this old man entertained and on my feet and to: Mr. Arthur Winter for introducing me to country music; Mrs. Rebecca Pease for her magnificent story telling about spheres; Mr. Brian Borak and his automated board of shame, and Ms. Rebecca Vieira, for kicking me out of my hood. Me gustaría dar las gracias a la Srta. Susana iii López Sola por ser muy simpática y “cool”. Mostly, I owe a great deal of thanks to Ms. Rebecca Vieira for teaching me how to read and write, how to use a computer, and for editing this dissertation twice. I am thankful for my good friends outside of the Falvey group. These people include Dr. Suzanne Bogaczyk, for being my twin, Dr. Z. Serpil Gönen-Williams, and Dr. Banu Keşanlı for being the heart and soul of the department when I started at Maryland and welcoming me into the Maryland family. I am thankful to Dr. William McElroy, Dr. Melanie Moses, and Dr. William Seganish Jr. for being such great friends over the past years. I am most thankful to and for Mrs. Jennifer Seganish, for being my best friend and partner in crime over the past three years. I’ll miss you most of all, scarecrow and I’ll get you and your little baby, too. I hope someday that you do land your favorite pair of jeans, Yee-haw! I would be remiss if I did not mention the Wednesday night dinner crew and the EUropean CHemistry REview club for keeping me both on and off task, as I finished this dissertation. Outside of the department, many friends have helped keep me sane and insane during my time in graduate school. I owe many thanks to Ms. Stacy McIlhenny, who has been my best friend ever since middle school, for putting up with me for the past 15 years. Stace, thanks for being there whenever, wherever, and always. I would like to say a very special thank you to LCDR Matthew Lee, USN and Clarence, the bloodhound. I really appreciated the much needed weekend vacations during my last years in graduate school. You really kept me going, even when I wanted to stop. Go Navy, Beat Army! iv TABLE OF CONTENTS TABLE OF CONTENTS ................................................................................................. v LIST OF FIGURES ........................................................................................................ xii LIST OF SCHEMES ..................................................................................................... xix LIST OF TABLES ....................................................................................................... xxiv Chapter 1: Nitrenium Ions............................................................................................... 1 1.1: Nitrenium Ions Defined ............................................................................................ 1 1.2: Reactions of the Singlet and Triplet States............................................................... 6 1.3: Historical Background ............................................................................................. 8 1.4: Gassman’s Studies.................................................................................................. 12 1.5: Contemporary Studies............................................................................................ 23 1.6: Recent Falvey Group Research.............................................................................. 31 1.7: Conclusions ............................................................................................................ 36 1.8: References .............................................................................................................. 37 Chapter 2: Laser Flash Photolysis ................................................................................ 47 2.1: Brief History of Laser Flash Photolysis................................................................ 47 2.2: Photochemical Methods to Generate Nitrenium Ions............................................ 48 2.3: Laser Flash Photolysis – Time-Resolved Ultraviolet-Visible (LFP-TRUV) .......... 51 v 2.4: References .............................................................................................................. 64 Chapter 3: Photogenerated N-Methyl-N-(1-naphthyl)nitrenium Ion and N-Methyl- N-(2-naphthyl)nitrenium Ion ......................................................................................... 70 3.1: Carcinogenic History ............................................................................................. 70 3.2: N-Methyl-N-1-naphthylnitrenium ion .................................................................... 97 3.2.1: N-Methyl-N-1-naphthylnitrenium ion: History and Introduction .................... 97 3.2.2: Synthesis of Photochemical Precursor to the Nitrenium Ion ........................... 99 3.2.3: Stable Photoproducts....................................................................................
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