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Molybdenum Oxotransferase Active Site Models and Their Oxygen Atom

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Molybdenum Oxotransferase Active Site Models and Their Oxygen Atom Molybdenum Oxotransferase Active Site Models and Their Oxygen Atom Transfer Reactivity By Lee Taylor Elrod B.S. University of Vermont 2010 A Dissertation Submitted in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy in the Department of Chemistry at Brown University Providence, Rhode Island, May 2018 © Copyright 2018 Lee Taylor Elrod This dissertation by Lee Taylor Elrod is accepted in its present form by the Department of Chemistry as satisfying the dissertation requirement for the degree of Doctor of Philosophy Recommended to the Graduate Council Date____________ _____________________________ Eunsuk Kim, Ph.D. Advisor Date____________ _____________________________ Jerome Robinson, Ph.D. Reader Date____________ _____________________________ Paul Williard, Ph.D. Reader Approved by the Graduate Council Date____________ _____________________________ Andrew G. Campbell, Ph.D. Dean of the Graduate School iii Curriculum Vitae Lee Taylor Elrod Education: PhD Inorganic Chemistry with Dr. Eunsuk Kim 2018 Brown University, Providence, RI B.S. Degree in Chemistry 2010 University of Vermont, Burlington, VT High School Diploma 2006 Libertyville High School, Libertyville, IL Academic Accomplishments: • Dissertation Fellowship, Brown University • Recipient Charles E. Braun Award, University of Vermont • Recipient Clinton D. Cook Award in Chemistry, University of Vermont • Recipient Presidential Scholarship (2006-2010), University of Vermont • Recipient Academic Excellence Scholarship (2006-2010), University of Vermont Presentations: Elrod, L. T.; Kim, E. “Oxygen Atom Transfer Mediated By Molybdenum Oxo Complexes and Lewis Acid”. Poster presentation at 252nd ACS National Meeting & Exposition, Philadelphia, PA, August 2016 Publications: • Elrod, L. T.; Robinson, J. R.; Victor, E.; Kim, E. “Lewis Acid Enhanced Nitrate and Perchlorate reduction by Mo(µ-O) Dimer” Manuscript in preparation. • Elrod, L. T.; Kim, E. “Lewis Acid Assisted Nitrate Reduction with Biomimetic Molybdenum Oxotransferase Complex” Inorg. Chem. 2018, 57, 2594 -2602. • Cao, R.; Elrod, L. T.; Lehane, R. L.; Kim, E.; Karlin, K.D. “A Peroxynitrite Dicopper Complex: Formation via Cu–NO and Cu–O2 Intermediates and Reactivity via O–O Cleavage Chemistry” J. Am. Chem. Soc., 2016, 138, 16148-16158. iv • Roering, A. J.; Elrod, L. T.; Pagano, J. K.; Guillot, S. L.; Chan, S. M.; Tanski, J. M.; Waterman, R. “A General Synthesis of Phosphaalkenes at Zirconium with Liberation of Phosphaformamides” Dalton Trans. 2013, 42, 1159-1167. • Elrod, L. T.; Boxwala, H.; Haq, H.; Zhao, A. W.; Waterman, R. “As-As Bond Formation Via Reductive Elimination from a Zirconocene Bis(dimesitylarsenide) Compound” Organometallics, 2012, 31, 5204-5207. • Roering, A. J.; Maddox, A. F.; Elrod, L. T.; Chan, S. M.; Ghebreab, M. B.; Donovan, K. L.; Davidson, J. J.; Hughes, R. P.; Shalumova, T.; MacMillan, S. N.; Tanski, J. M.; 3– Waterman, R. "General Preparation of (N3N)ZrX (N3N = N(CH2CH2NSiMe3)3 ) Complexes from a Hydride Surrogate" Organometallics, 2009, 28, 573-581. Teaching Experience: 2012 to Present Brown University, Department of Chemistry Providence, RI Fall 2015: • Head teaching assistant advanced undergraduate inorganic lab, 1 section Spring 2014: • Head teaching assistant undergraduate bioinorganic lab, 2 sections Fall 2013: • Head teaching assistant advanced undergraduate inorganic lab, 1 section per Spring 2013: • Teaching assistant undergraduate bioinorganic lab, 2 sections Fall 2012: • Teaching assistant undergraduate general chemistry laboratory, 1 section 2011-2012 University of Vermont Department of Chemistry Burlington, VT • Teaching assistant undergraduate general chemistry laboratory, 5 sections per semester • Teaching assistant undergraduate inorganic chemistry, one section Spring 2012 • Oversaw and assisted undergraduate and high school researchers in lab affiliated with NOYCE scholarship/ACS Project SEED 2010 Indiana University Bloomington, IN • Graduate teaching assistant for organic chemistry laboratory 2009 University of Vermont Department of Chemistry Burlington, VT • Teaching assistant for general chemistry laboratory, 2 sections v Acknowledgments I would like to thank the following people for their help and contributions to this work. First, I would like to thank Dr. Eunsuk Kim. Over the past five and half years she has help me continue to develop as a scientist. Her continued support and insight into my project is why I can present my work here. Her enthusiasm for bioinorganic chemistry and research has had a profound impact on how I approach research. Her encouragement has helped me overcome the day to day obstacles of research, and I am thankful for her support, guidance, and patience. I would also like to thank Dr. Jerome Robinson for his continued help with experimental techniques, discussions about science, and serving on my thesis V committee. The X-ray crystallography and structure determination of the Mo2 O3 complex presented here was solved by Dr. Robinson and was critical to the preparation of this thesis. Thank you to Dr. Paul Williard and Dr. Wesley Bernskoetter for serving as my committee members. Their insights and comments have fostered helpful discussions about my research. I would also like to thank Dr. Eric Victor for V computational work performed on the Mo2 O3 complex. Thank you to all the current and former Kim Group members. Last, and certainly not least. I would like to thank my parents Lee and Jackie Elrod. Without their love and support this would not have been possible. Through the wonderful and terrible times, they have always been there for me, and that makes me truly blessed. vi Table of Contents Signature Page iii Curriculum Vitae iv Acknowledgments vi Table of Contents vii List of Figures ix List of Schemes xv List of Equations xvi Chapter 1. Introduction 1 1.1. Introduction 2 1.2. Nitrate and Perchlorate 3 1.3. Nitrate and Perchlorate Reducing Enzymes 5 1.4. Biomimetic Nitrate Reducing Molybdenum Complexes 8 1.5. Perchlorate Reducing Complexes 11 1.6. Lewis Acid Additives and Oxygen Atom Transfer 13 1.7. References 16 Chapter 2: Lewis Acid Assisted Nitrate Reduction with Biomimetic 27 Molybdenum Oxotransferase Complex 2.1. Abstract 28 2.2. Introduction 29 2.3. Experimental Section 34 2.4. Results and Discussion 40 2.5. Conclusions 58 vii 2.6. References 59 Chapter 3: Structure and Oxygen Atom Transfer Reactivity of 70 Dinuclear (µ-O)Molybdenum(V) Complex 3.1. Abstract 71 3.2. Introduction 72 3.3. Experimental Section 76 3.4. Results and Discussion 82 3.5. Conclusions 105 3.6. References 106 Chapter 4: Lewis Acid Assisted Perchlorate Reduction with 112 Dinuclear Molybdenum(V)(µ-Oxo) Complex 4.1. Abstract 113 4.2. Introduction 114 4.3. Experimental Section 117 4.4. Results and Discussion 120 4.5. Conclusions 125 4.6. References 125 viii List of Figures Figure 1.1. Reduction of DMSO by DMSOR from Rhodobacter 6 sphaeroides. Figure 1.2. The global nitrogen cycle. 6 Figure 1.3. Reduced active sites of a) DMSOR from Rhodobacter 7 sphaeroides b) Nar from Escherichia coli and PcrAB from Azopira suillum c) Nap from D. desulfuricans , where Asp = aspartate, Cys = cysteine, and Ser = serine. Figure 1.4. OAT with Holm dithiolene DMSOR structural and 8 functional model complexes. Figure 1.5. Model complexes a) Mo2O3(5-SO3ssp)2(sol)2 b) Mo2O3(L- 9 NS2)2(sol)2, where sol = DMF. Figure 1.6. Proposed associative mechanism for nitrate reduction by 10 IV i [W (SC6H2-2,4,6-Pr 3)(S2C2Me2)2](Et4N). Figure 1.7. Catalytic nitrate reduction with 10 [Et4N][Mo(SPh)(PPh3)(mnt)2] and triphenylphosphine. V Figure 1.8. Catalytic perchlorate reduction with Re (O)(hoz)2Cl or 12 V [Re (O)(hoz)2(OH2)]OTf and organic sulfide. Cy II Figure 1.9. Nitrate reduction by N(afa )3Fe (OTf)](OTf). 13 Cy II Figure 1.10. Perchlorate reduction by N(afa )3Fe (OTf)](OTf). 13 v Figure 1.11. OAT from (TBP8Cz)Mn (O) to aryl phosphine 14 v Figure 1.12. Generation of valence tautomer from (TBP8Cz)Mn (O) and 15 •+ IV 2+ OAT with [(TBP8Cz )Mn (O)-Zn ]. 3+ V Figure 1.13. Proposed binding of Sc to [Mn (O)(TAML)][PPh4]. 16 Figure 2.1. Active site structures of the oxidized forms of periplasmic 30 nitrate reductase (Nap) from D. desulfuricans and formate dehydrogenases (Fdhs) from E. coli (X = SeCys) or R.capsulatus (X = Cys). VI IV Figure 2.2. Mo (O)2(SN)2 (1) and Mo (O)(SN)2 (SN=bis(4-t- 33 butylphenyl)-2-pyridylmethanethiolate) ix Figure 2.3. KBr IR of Mo(O)2(SN)2 (1) (yellow trace) and Mo(O)(SN)2 41 (2) 1 Figure 2.4a. Room temperature H NMR Mo(O)2(SN)2 (1) in CD2Cl2 42 1 Figure 2.4b. Room temperature H NMR Mo(O)2(SN)2 (1) in CD2Cl2. 43 1 Figure 2.5a. Room temperature H NMR Mo(O)(SN)2 (2) in CD2Cl2. 43 1 Figure 2.5b. Room temperature H NMR Mo(O)(SN)2 (2) in CD2Cl2. 43 Figure 2.6. Room temperature UV-vis of Mo(O)2(SN)2 (1) and 44 Mo(O)(SN)2 (2) in DCM. Figure 2.7. Room temperature UV-vis of Mo(O)(SN)2 (2) and 45 Bu3N(NO3) (10 equiv.) after 24 hours in DCM. Figure 2.8. Room temperature UV-vis of Mo(O)2(SN)2 (1) generated 46 from Mo(O)(SN)2 (2) (1 equiv.), Sc(OTf)3 (2 equiv.) and Bu4N(NO3) (10 equiv.) in DCM. Figure 2.9. KBr of Mo(O)2(SN)2 (1) generated from Mo(O)(SN)2 (2) (1 46 equiv.), Sc(OTf)3 (2 equiv.) and Bu4N(NO3) (10 equiv.) in DCM. 1 Figure 2.10. H NMR of Mo(O)2(SN)2 (1) generated from Mo(O)(SN)2 47 (2) (1 equiv.), Sc(OTf)3 (2 equiv.) and Bu4N(NO3) (10 equiv.) and authentic Mo(O)2(SN)2 (1). Figure 2.11. Reaction of Mo(O)(SN)2 (2) (0.8 mM), [Bu4N][NO3] (8.0 48 mM), and Sc(OTf)3 (1.7 mM) followed by UV-Vis spectroscopy at –40 ºC in dichloromethane for 1.5 hours.
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