The Chemistry of Solvated Nitric Oxide: As the Free Radical and as Super-saturated Dinitrogen Trioxide Solutions By Kristopher A. Rosadiuk March, 2015 A thesis submitted to McGill University in partial fulfillment of the requirements in the degree of: DOCTORATE OF PHILOSOPHY Department of Chemistry, Faculty of Science McGill University Montreal, Quebec, Canada © Kristopher Rosadiuk, 2015. Abstract The unusual behaviour of the mid-oxidation state nitrogen oxides, nitric oxide (NO) and dinitrogen trioxide (N2O3), are explored in solution. Nitric oxide is shown to catalyze the cis-trans isomerizations of diazo species in aqueous and organic solutions, and a model is presented by which this proceeds by spin catalysis, making use of the unpaired electron of NO to permit access to triplet patways. Five diazo compounds are tested and compared to stilbene, which is not found to isomerize under these conditions. Dinitrogen trioxide is found to form easily in organic solvents, which stabilize the molecule even above room temperature. Solutions can be formed at chemically useful concentrations and levels of purity, and this result is compared with the sparse literature concerning this phenomenon. The chemistry of these solutions at 0˚C is surveyed extensively, with 23 distinct organic reactions and 15 inorganic reactions being described. The first reported room temperature adduct of dinitrogen trioxide is presented, as well as novel syntheses for nitrosyl chloride and nitrosylsulfuric acid. X-ray structures are also given for a previously reported benzoquinone-phenol adduct, as well as a new mixed valent-mercury nitride salt of the form Hg4N4O9. Résumé Le comportement inhabituel des oxydes d'azote aux états d’oxydations moyens, comme l’oxyde nitrique (NO) et le trioxyde dinitrique (N2O3), est exploré en solution. II L'oxyde nitrique s’avère à catalyser les isomerizations cis-trans des espèces diazoïques dans les solutions aqueuses et organiques. Un modèle est présenté dans lequel le procédé est accomplie via catalyse de spin, par l’entremisse d’un électron non-apparié de l’oxyde nitrique qui donne accès aux états triplets. Cinq composés diazoïques sont testés et comparés avec le stilbene, qui ne s’isomérise pas dans ces conditions. Le trioxyde dinitrique s’avère à se former facilement dans les solvants organiques, qui stabilisent la molécule même au-dessus de la température ambiante. Les solutions peuvent être synthétisées à concentrations chimiquement utile et suffisamment pures, et ce résultat est comparé avec le nombre faible des littératures concernant ce phénomène. La chimie de ces solutions au 0˚C est explorée en profondeur, décrivant 23 réactions organiques distinctes et 15 réactions inorganiques décrites. La première synthèse reportée d'un adduit du trioxyde dinitrique qui demeure stable à température ambiante est présentée, en plus de synthèses originales pour le chlorure de nitrosyl et de l'acide nitrosylsulfurique. Les structures en Rayons-X sont aussi présentées pour l'adduit bezoquinone-phenol antécédemment reporté, ainsi qu’un nouveau composé à valence mixte d'un sel de nitrure de mercure sous la forme Hg4N4O9. III Dedicated to my parents, John and Kathy who thought it was fine to let me keep powdered charcoal, sulfur, and potassium nitrate in my room, next to the stuffed animals and bones. and to J.W. Mellor: Right back at you, Sarge. IV Acknowledgements This work would not exist without the support, purposeful or unwitting, of many people. I would like to thank McGill University and associated agencies for the funding and support, and to the faculty and staff of the Chemistry Department for making this a hospitable place in which to while away the years. Special thanks to: Chantal Marotte, for always stepping up to bat for bewildered grad students; Fred Morin, Alex Wahba, J.P. Guay, Rick Rossi and Weihua Wang for making sure that things were working; Mario Perrone and Claude Perryman for making sure there was something to work with; and Samuel Lewis Sewall for the Raman and the cool. Thank you to all of my lab mates past and present, for forming the intellectual humus in which science actually takes root and grows. Erin Dodd, Inna Peripichka, ZJ Chua, and Joel Poisson have all taught me a thing or ten, and have been good friends over the years. An extra thank you to ZJ for the tremendous help with the X-ray diffraction, and one more for my thesis editors (ZJ, Erin, Tina, and Dr. Bohle). Marie-Jose Bellemare, Wei Gu, Cheryl Bain, Laura Brothers, and Mirna Paul have all gone on without me, but we had some good fun. Thank you to Ivor Wharf for the stories and the know-how, and to Tina Lam for the pep talks, cider, and help translating the abstract. To all the post-docs and undergrads: thanks for the opportunity to be a teacher, and I swear I do remember you, even if I can't remember your name six months from now. V To my supervisor Dr. Scott Bohle, I'll just say: thank you for being what I always thought a scientist should be, and for inspiring me to stick with it, and for your understanding of what was really important. The food was good too. To my family, my parents, grandparents, brother, sisters, aunts and uncles and cousins, the Rosadiuks and Mykytiuks and Bezborodkas and the weird offshoots of the clan, here today and departed: thank you for your patience, your indulgence, your interest, and all the hardship you endured so that I could spend my days playing with blue liquids. Thank you for putting this in perspective. And of course, the food was good too. Lastly, my thanks to Dominique Ferraton: for her faith, and for what she saw whenever we went out looking. VI Contribution Of Authors This dissertation contains the work of a submitted manuscript, in Chapter 2: Nitric Oxide Catalysis of Diazene cis-trans Isomerization. D. Scott Bohle, Kristopher Rosadiuk, Inorganic Chemistry. All DFT calculations were carried out by D. Scott Bohle. All other work was carried out solely by the author under the supervision of Professor D. Scott Bohle. VII Table of Contents Table of Figures ................................................................................................................................... X Table of Equations ........................................................................................................................... XII Table of Tables ............................................................................................................................... XIII Prologue ....................................................................................................................................... 1 Chapter 1: An Introduction to the Oxides of Nitrogen ................................................. 6 1.2 Summary ...................................................................................................................................... 21 General Experimental ...........................................................................................................24 Chemicals ............................................................................................................................................ 24 Spectroscopy/Analysis .................................................................................................................. 25 Methods ............................................................................................................................................... 26 Preparation of Trioxide Solutions ............................................................................................. 27 Handling of Trioxide Solutions ................................................................................................... 27 Chapter 2: Nitric Oxide Catalysis of Diazene cis-trans Isomerization ..................29 2.1 Introduction to spin catalysis .............................................................................................. 29 2.2 Experimental .............................................................................................................................. 33 Diazo preparation ....................................................................................................................................... 34 Isomerization protocol ............................................................................................................................. 36 Nitric oxide preparation ........................................................................................................................... 36 Solution treatment ...................................................................................................................................... 38 Measurement ................................................................................................................................................ 39 2.3 Theoretical methods ............................................................................................................... 40 2.4 Experimental results ............................................................................................................... 40 2.5 Theoretical results ................................................................................................................... 47 2.6 Discussion ................................................................................................................................... 48 Mode of NO association ...........................................................................................................................