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University of Oklahoma Graduate College UNIVERSITY OF OKLAHOMA GRADUATE COLLEGE SYNTHESIS AND REDOX BEHAVIOR OF GROUP 8 METALLOPORPHYRINS AND RELATED COMPOUNDS A DISSERTATION SUBMITTED TO THE GRADUATE FACULTY in partial fulfillment of the requirements for the Degree of DOCTOR OF PHILOSOPHY By DENNIS AWASABISAH Norman, Oklahoma 2015 SYNTHESIS AND REDOX BEHAVIOR OF GROUP 8 METALLOPORPHYRINS AND RELATED COMPOUNDS A DISSERTATION APPROVED FOR THE DEPARTMENT OF CHEMISTRY AND BIOCHEMISTRY BY ______________________________ Dr. George B. Richter-Addo, Chair ______________________________ Dr. Kenneth M. Nicholas ______________________________ Dr. Daniel T. Glatzhofer ______________________________ Dr. Mark A. Nanny ______________________________ Dr. Robert Thomson © Copyright by DENNIS AWASABISAH 2015 All Rights Reserved. Dedications I dedicate this work to my dad, the late Bonaventure Akowiak Awasabisah, my mum, Mary Azongpok Awasabisah, my wife, Maa Ahema Awasabisah and daughters, Phoebe and Denise Awasabisah. Acknowledgements I would like to express my sincere appreciation to my advisor, Dr. George Richter-Addo for being the best mentor I could ask for. Thanks for the insightful research discussions we have had and for challenging me to undertake independent work. You have taught me to ask the right questions and be critical of my own work. As you always put it, “People will never remember how long it took to complete a job, but they will always remember how well you did the job.” Thanks for all your counsel. I would also like to thank my advisory committee; Dr. Kenneth Nicholas, Dr. Daniel Glatzhofer, Dr. Mark Nanny, and Dr. Robert Thomson, for their guidance and support throughout my studies. I would also like to thank Dr. David Nagle and Dr. Robert Houser who previously served as members of my advisory committee. I learnt so much from you all. Thanks to both past and present members of the GBRA group; Dr. Nan Xu, Dr. Jun (Eva) Yi, Dr. Myron W. Jones, Dr. Adam Warhausen, Guan Ye, Bing Wang, Erwin Abucayon, Samantha Powell, Neda Hessami and Wenhua Wang. It was such a great privilege to have worked with you. All the times we shared talking about science and life in general were priceless. I consider you all as part of my family and I wish to continue to keep in touch with you. Thanks Ye with help with the DFT calculations. I would also like to thank our research collaborator, Dr. Michael J. Shaw for all the interesting research discussions we have had, and for his help in kick-starting my pursuit of the Ph.D. Chemistry degree program when I was a student at SIUE. I am grateful to Dr. Michael J. Shaw and Krishna P. Sharmah Gautam for their contribution in Chapter 2 and for providing preliminary data on the synthesis and electrochemistry of iv the (por)Ru(NO)(OC(=O)Fc) complexes. My next special gratitude also goes to the research support staff at OU; to Dr. Douglas Powell for his help with my crystallographic work; Dr. Susan Nimmo for help with NMR spectroscopy; Dr. Steve Foster with help with mass spectrometry; Jim Cornell for all the glass-blowing jobs as well as Chad and Carl in the electronic shop for all their help. Last but not least, I would like to thank my dear wife, Maa Ahema for her love, encouragement and patience throughout my academic career. I am truly blessed by her support through the years. Special thanks to my parents, and siblings; Diana, Cordelia, Martin and Tony for all the love and support they have shown me throughout my life and for teaching me to be disciplined. v Table of Contents Acknowledgements ......................................................................................................... iv List of Tables ................................................................................................................... xi List of Figures ................................................................................................................ xiii Abstract ................................................................................................................ xxvi Chapter 1 Linkage Isomerization in Metal complexes ............................................. 1 1.1 Introduction .......................................................................................................... 1 1.1.1 Modes of binding of NOx moieties in monometallic complexes ................. 3 1.1.1.1 Nitric oxide (NO) complexes ....................................................... 3 1.1.1.2 NO2 Complexes ............................................................................ 5 1.1.1.3 NO3 Complexes ............................................................................ 5 1.1.2 Methods that induce linkage isomerization ................................................. 6 1.1.3 Techniques for detecting linkage isomers ................................................... 6 1.1.4 Factors that affect linkage isomerization ..................................................... 7 1.2 Linkage isomerism in non-porphyrin NOx complexes ......................................... 9 1.2.1 Group 6 (Cr and Mo) complexes ................................................................. 9 1.2.1.1 NO complexes .............................................................................. 9 1.2.1.2 NO2 complexes ........................................................................... 12 1.2.2 Group 7 (Mn and Re) complexes .............................................................. 14 1.2.2.1 NO complexes ............................................................................ 14 1.2.3 Group 8 (Fe, Ru and Os) complexes ......................................................... 17 1.2.3.1 NO complexes ............................................................................ 17 vi 1.2.3.2 NO2 complexes ........................................................................... 22 1.2.3.3 NO3 complexes ........................................................................... 25 1.2.4 Group 9 (Co, Rh and Ir) complexes .......................................................... 27 1.2.4.1 NO complexes ............................................................................ 27 1.2.4.2 NO2 complexes ........................................................................... 28 1.2.5 Group 10 (Ni, Pd and Pt) complexes ......................................................... 30 1.2.5.1 NO complexes ............................................................................ 30 1.2.5.2 NO2 complexes ........................................................................... 32 1.3 Linkage isomerism in NOx-coordinated metalloporphyrins ............................... 37 1.3.1 Manganese NOx porphyrins ....................................................................... 39 1.3.2 Ruthenium and iron NOx porphyrin complexes ........................................ 49 1.3.3 Cobalt NOx porphyrins .............................................................................. 58 1.3.4 Hyponitrite complexes of transition metal porphyrins .............................. 61 1.3.4.1 The nitric oxide dimer and its reduced forms ............................. 66 1.3.4.2 Metal hyponitrite binding modes ................................................ 71 1.4 Heme proteins ..................................................................................................... 93 1.5 Conclusion ........................................................................................................ 103 1.6 References ........................................................................................................ 104 Chapter 2 Synthesis, Characterization and Redox Behavior of Stable Ruthenium Nitrosyl Complexes with Axial O-Bound Ligands ............................. 120 2.1 Introduction ...................................................................................................... 120 2.2 Experimental Section ........................................................................................ 121 2.2.1 Chemicals ................................................................................................ 122 vii 2.2.2 Instrumentation/ Spectroscopy ................................................................ 122 2.2.3 Syntheses ................................................................................................. 124 2.2.3.1 Preparation of (T(p-OMe)PP)Ru(NO)(OC(=O)CH3) (1) ......... 124 2.2.3.2 Preparation of (T(p-OMe)PP)Ru(NO)(OC(=O)CH(CH3)2) (2) 125 2.2.3.3 Preparation of (T(p-OMe)PP)Ru(NO)(OC(=O)C(CH3)3) (3) .. 126 2.2.3.4 Preparation of (T(p-OMe)PP)Ru(NO)(OC(=O)(C6H4-p-NO2) (4) .............................................................................................................. 126 2.2.3.5 Preparation of (T(p-OMe)PP)Ru(NO)(OC(=O)Fc) (5) ............ 127 2.2.3.6 Preparation of (TTP)Ru(NO)(OC(=O)Fc) (6) .......................... 128 2.2.3.7 Preparation of (T(p-OMe)PP)Ru(NO)(OC6HF4) (7) ................ 129 2.2.3.8 Preparation of (T(p-OMe)PP)Ru(NO)(OC(=O)CF3) (8).......... 130 2.3 Results and Discussion ..................................................................................... 131 2.3.1 Synthesis .................................................................................................. 131 2.3.2 Mass Spectrometry .................................................................................. 132 2.3.3 Infrared Spectroscopy and Monitoring Reactions ................................... 133 2.3.4 1H NMR and 19F NMR Spectroscopy ...................................................... 140 2.3.5 X-ray
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