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SYNTHESIS and PROPERTIES of NON-HEME IRON-Nox COMPLEXES for THE

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SYNTHESIS and PROPERTIES of NON-HEME IRON-Nox COMPLEXES for THE SYNTHESIS AND PROPERTIES OF NON-HEME IRON-NOx COMPLEXES FOR THE GENERATION OF NITROXYL DONORS AND NITRITE REDUCTION CATALYSTS by BRIAN CLARK SANDERS (Under the Direction of Todd C. Harrop) ABSTRACT The biological interplay between Fe and NyOx is significant to both human physiology and the remediation of global pollution. The interconversion of NyOx species is primarily mediated by metalloenzymes, in which Fe plays a critical role. Due to their critical role in biology and the environment, the study of Fe-NyOx interactions is of fundamental interest in coordination chemistry. Additionally, thiol-containing biomolecules have direct interaction with Fe-NyOx. For example, Fe(III)-NO2 complexes react with thiols to NO or HNO and the corresponding sulfenic acids. Given the complex interplay between NyOx, Fe, and thiols, there is a need to rationalize this intricate chemistry through model complexes. Our approach involves the design and synthesis of modular non-heme complexes in which donor strength, flexibility, and secondary-sphere interactions are readily tuned. This methodology has facilitated the 8 isolation and characterization of the first non-heme {FeNO} and Fe(II)(NO2)2 complexes, and allowed for the first study of their reactivity with Fe(III)-porphyrins, Fe(III)-myoglobin, thiols, and protons. From these reactivity studies we have demonstrated nitroxyl-transfer to metMb to give MbNO, thus outlining the proof-of-principle for the rational design of metal-based HNO donors. Moreover, we have demonstrated that reactions of non-heme {FeNO}7/8 complexes with thiols ultimately leads to various dinitrosyl iron complexes (DNICs) in an oxidation state dependent manner. These results suggest a possible route to DNIC formation from non-heme 7/8 {FeNO} complexes in biology. Lastly, the development of non-heme NO2 reduction catalysts + is discussed. In the presence of H /thiols the selective and catalytic conversion of NO2 to NO(g) is observed. However, in the presence of only thiols, a net three-electron reduction of Fe(II)(NO2)2 to the Fe(I)(NO)2 DNIC is observed, and suggests a possible role for Fe-NO2 and thiols in the formation of biological DNICs. Described in this dissertation is the synthesis, characterization, and reactivity of a series of non-heme Fe-NOx complexes, which provides the basis for the development of non-heme NO2 reduction catalysts and Fe-based HNO donor molecules for the purpose of cardiovascular therapies and environmental remediation. INDEX WORDS: Nitroxyl, Nitrite, Iron, Non-heme, Nitric Oxide SYNTHESIS AND PROPERTIES OF NON-HEME IRON-NOX COMPLEXES FOR THE GENERATION OF NITROXYL DONORS AND NITRITE REDUCTION CATALYSTS by BRIAN CLARK SANDERS B.S., University of Tennessee, 2008 A Dissertation Submitted to the Graduate Faculty of The University of Georgia in Partial Fulfillment of the Requirements for the Degree DOCTOR OF PHILOSOPHY ATHENS, GEORGIA 2015 © 2015 Brian Clark Sanders All Rights Reserved SYNTHESIS AND PROPERTIES OF NON-HEME IRON-NOX COMPLEXES FOR THE GENERATION OF NITROXYL DONORS AND NITRITE REDUCTION CATALYSTS by BRIAN CLARK SANDERS Major Professor: Todd C. Harrop Committee: Michael K. Johnson Jeffrey L. Urbauer Electronic Version Approved: Julie Coffield Interim Dean of the Graduate School The University of Georgia May 2015 ACKNOWLEDGEMENTS I would like to thank my advisor, Professor Todd C. Harrop, for his support and willingness to take a chance on a me. I also thank Todd for introducing me to the field of bioinorganic chemistry, an area that I expect to always be of interest and pursuit in my future research. Todd's willingness to guide students and teach them the proper way to traverse an academic/research landscape is, and will be, exceptionally valuable to me in my future career. I look forward to watching the Harrop laboratory continue to grow and thrive. I would also like to thank Prof. Michael K. Johnson and Prof. Jeffrey L. Urbauer and their labs for support and assistance with EPR and NMR, respectively. Moreover, I would like to thank MKJ and JLU for their guidance and genuine support as members of my graduate committee. Thank you for your letters of recommendation and continued support. I would also like to thank Dr. Phillips for assistance with MS experiments, Dr. Wei for assistance with X-ray diffraction, Dr. Wylie, Dr. Cui, and Henry Niedermaier for assistance with NMR, Brian Vaccaro for assistance with EPR, and Dr. Hassan for assistance with GC-MS. I would also like to thank Dr. Jay Agarwal for his collaborative nature and scientific curiosity. I would like to thank my group members past and present. Thank you Dr. Ashis K. Patra and Koustubh Dube for your seminal work in the Harrop lab from which I was able to expand upon with my own research projects. Thank you Dr. Eric Gale for your mentality and creative chemical mind, you are an inspiration and excellent researcher. I look forward to future science and discussions with you. Thank you to Dr. Vivian Ezeh for your wonderful attitude and iv persistence as a researcher, you taught me many things and importantly served as an excellent role model in the pursuit of both teaching and researching chemistry. I look forward to following your career and future achievements. Thank you for your support. Thank you to my current lab members: Ellen Broering, Melody Rhine, Ramsey Steiner, and Phan Truong for your support, collaboration, and teamwork. It has truly been a pleasure working with all of you and I thank you for your selflessness and your ever-present willingness to help one another. I can only hope I helped you all equal to that in which you helped me. I truly could not have done it without you. I would like thank my wonderful family: my parents George and Cheryl Sanders, brother John, sister-in-law Ali, nephew Eli, aunt Kila, Uncle Michael, cousins Meghan and Laura, and Grandmother Ina Lima for their love and support. I love you all very much and would not be where I am today without you. Thank you all! v TABLE OF CONTENTS Page CHAPTER 1 INTRODUCTION AND LITERATURE REVIEW .....................................................1 1.1 An Overview: Nitrogen Oxides and the Nitrogen Cycle ...................................1 1.2 An Overview: Nitrogen Oxides and Mammals .................................................5 1.3 An Overview: Nitrogen Oxides and the Environment .......................................9 1.4 The Coordination Chemistry of HNO, NO, and NO2 with Iron .....................11 n 1.5 The {FeNO} (n = 6, 7, 8) Formulation in Biology .........................................18 1.6 Nitroxyl (NO /HNO) Chemistry and Pharmacology .......................................31 8 1.7 {FeNO} Heme Coordination Complexes .......................................................41 8 1.8 {FeNO} Non-heme Coordination Complexes ................................................62 1.9 Nitrite in Biology .............................................................................................75 1.10 Heme Fe(NO2) Model Complexes .................................................................89 1.11 Reactivity of Heme Fe(II/III) Complexes ....................................................108 1.12 Non-heme Fe(NO2) Model Complexes .......................................................120 1.13 Research Objective and Purpose ..................................................................131 1.14 References ....................................................................................................133 vi 2 SYNTHESIS, PROPERTIES, AND REACTIVITY OF A SERIES OF NON-HEME {FeNO}7/8 COMPLEXES: IMPLICATIONS FOR Fe-NITROXYL COORDINATION .....................................................................................................156 2.1 Abstract ..........................................................................................................157 2.2 Introduction ....................................................................................................158 2.3 Results and Discussion ..................................................................................163 7 2.4 Spectroscopic and Electrochemical Properties of {FeNO} Complexes .......169 8 2.5 Synthesis and Spectroscopic Properties of {FeNO} Complexes .................173 7 8 2.6 Reactivity of {FeNO} and {FeNO} Complexes .........................................177 2.7 Conclusions ....................................................................................................197 2.8 Materials and Methods ...................................................................................199 2.9 Supporting Information ..................................................................................217 2.10 References ....................................................................................................244 3 NO2 ACTIVATION AND REDUCTION TO NO BY A NON-HEME Fe-(NO2)2 COMPLEX ..............................................................................................................250 3.1 Abstract ..........................................................................................................251 3.2 Introduction ....................................................................................................252 3.3 Spectroscopic and Reactive Studies of Complex 1MeCN and 2 ......................253 3.4 Reactive Studies of 2 .....................................................................................256 3.5 Conclusions ....................................................................................................261
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