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An Experimental and Computational Comparison of the Reactions of N2O and CO2 in Several Inorganic Systems

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An Experimental and Computational Comparison of the Reactions of N2O and CO2 in Several Inorganic Systems Please do not remove this page An Experimental and Computational Comparison of the Reactions of N2O and CO2 in Several Inorganic Systems Davis, Jack Vickery https://scholarship.miami.edu/discovery/delivery/01UOML_INST:ResearchRepository/12386108050002976?l#13386108040002976 Davis, J. V. (2021). An Experimental and Computational Comparison of the Reactions of N2O and CO2 in Several Inorganic Systems [University of Miami]. https://scholarship.miami.edu/discovery/fulldisplay/alma991031605661102976/01UOML_INST:ResearchR epository Open Downloaded On 2021/10/02 02:14:36 -0400 Please do not remove this page UNIVERSITY OF MIAMI AN EXPERIMENTAL AND COMPUTATIONAL COMPARISON OF THE REACTIONS OF N2O AND CO2 IN SEVERAL INORGANIC SYSTEMS By Jack Vickery Davis A DISSERTATION Submitted to the Faculty of the University of Miami in partial fulfillment of the requirements for the degree of Doctor of Philosophy Coral Gables, Florida August 2021 ©2021 Jack Vickery Davis All Rights Reserved UNIVERSITY OF MIAMI A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy AN EXPERIMENTAL AND COMPUTATIONAL COMPARISON OF THE REACTIONS OF N2O AND CO2 IN SEVERAL INORGANIC SYSTEMS Jack Vickery Davis Approved: ________________ _________________ Carl D Hoff, Ph.D. Roger M. Leblanc, Ph.D. Professor of Chemistry Professor of Chemistry ________________ _________________ Burjor K. Captain, Ph.D. Guillermo Prado, Ph.D. Associate Professor of Chemistry Dean of the Graduate School ________________ Manuel Temprado, Ph.D. Associate Professor of Chemistry University of Alcalá DAVIS, JACK VICKERY (Ph.D., Chemistry) An Experimental and Computational Comparison of the (August 2021) Reactions of N2O and CO2 in Several Inorganic Systems Abstract of a dissertation at the University of Miami. Dissertation supervised by Professor Carl D. Hoff. No. of pages in text. (129) A series of four inorganic systems were examined to gain insight into the complex bonding patterns of nitriles, CO2 and N2O and their potential to be used as a chemical feedstock. In the first system, a thorough computational comparison of nitriles (RCN) t t binding to V(N[ Bu]Ar)3 (VL3) and Mo(N[ Bu]Ar)3 (MoL3) (Ar=3,5-Me2C6H3) revealed the importance of the ligand environment and electronic state. In the first complex, kinetic measurements of various nitriles (RCN) binding to VL3 revealed two distinct binding mechanisms dependent on R. Unencumbered aryl nitriles such as C6H5CN and 2,6-F2C6H3CN bound by an associative mechanism drawn from thermodynamically favorable π-interactions between the arene of the nitrile and anilide ligand. This is reflected in their experimentally determined activation parameters, having a relatively low ∆H‡ (~3 kcal/mol) but a more negative ∆S‡ (-27 cal/mol K). Alkyl nitriles such as MeCN and AdCN cannot make these favorable interactions and bind with a relatively higher ∆H‡ (7 kcal/mol) but a lower ∆S‡ (-10 cal/mol K). The net of these effects resulted in nearly identical ∆G‡ (9 kcal/mol) at -40°C. The reactivity of (R3Sn)2O (R= Ph, Cy) toward N2O and CO2 was examined in a detailed experimental and computational study. N2O binding to (R3Sn)2O to form trans- (R3Sn)2N2O2 is predicted to be unfavorable at all temperatures for both Ph and Cy derivatives. The rate and activation parameters of the reverse reaction of N2O extrusion from trans-(R3Sn)2N2O2 was studied through thermal decomposition of the hyponitrite complexes in an FTIR cell. CO2 was found to reversibly bind to (R3Sn)2O for both Ph and Cy at room temperature to form their respective (R3Sn)2CO3. Both of these reactions were studied computationally and a mechanism for both is proposed. Kinetic studies on the carboxylative cyclization of a propargylamine by Au(IPr)X were performed to gain insights into the mechanism of CO2 incorporation by a gold catalyst. A variety of experiments were run to determine optimal reaction conditions, mechanistic details and activation parameters. An important vinyl gold intermediate was synthesized and characterized crystallographically. The relative reaction rates of different gold compounds [Au(IPr)X] X= (Cl, vinyl) and [Au2(L)X2] were compared, with the digold achieving the highest reaction rates. The mechanochemical milling of Na2O and N2O in the presence of other additives is reported. Mechanochemical milling of these samples produces cis-Na2N2O2 in moderate yields at room temperature in few hours. Further milling leads to production of NaNO3 at yields approaching 50% after 50 hours. This work represents the first total oxidation of nitrous oxide to nitrate and may significant industrial relevance. Acknowledgements The work herein would not have been possible without the endless help from my family. I thank my wife Cristina for constantly pushing me forward and supporting me in more ways than I can count. I thank my parents for always being there for me and pushing me since I was a little boy and for always supporting me in all my life choices. I thank my mentor and advisor Dr. Carl Hoff for his constant support over the past five years. Without his mentorship and guidance this work would not have been possible. Through the early struggles of reactions that did not go as planned to our current more successful work I learned many lessons that will help me throughout my career and have shaped me into being a more resilient and well-rounded individual. I thank Dr. Burjor Captain for his useful suggestions in obtaining quality crystals and his work in solving our crystal structures and I thank Dr. Manuel Temprado for large theoretical and computational contributions and his computational chemistry mentorship. I also like to thank the students who have helped me along the way. From my first two years I thank Leo for his mentorship in computational chemistry and making beautiful figures. I thank Mohan for his endless help in our weeks long reactions and many crystallographic analysis attempts. I thank Oswaldo for his help in our mixer mill studies and for forcing me to learn how to teach again. Finally, I thank everyone at the University of Miami Chemistry Department for support and guidance when I needed it. iii TABLE OF CONTENTS Page LIST OF FIGURES ..................................................................................................... vi LIST OF SCHEMES.................................................................................................... xi LIST OF TABLES ....................................................................................................... xii Chapter 1: The Use of Catalysts to Produce Cleaner, More Efficient Reactions 1.1 Introduction and Purpose ............................................................................... 1 1.2 The Use of Transition Metals in Small Molecule Activation……...………… 2 1.3 Reactions of N2, N2O and CO2……………………………………………. ... 4 Chapter 2: The Mechanism of Binding of Nitriles to VL3 and ML3 Complexes 2.1 Background .................................................................................................... 8 2.2 Results and Discussion .................................................................................... 10 2.3 Conclusion ....................................................................................................... 32 2.4 Experimental Details ........................................................................................ 33 Chapter 3: Comparative Pathways for Elimination of N2O or CO2 from Trialkyltin Hyponitrites and Carbonates 3.1 Background .................................................................................................... 35 3.2 Results and Discussion .................................................................................... 37 3.3 Conclusion ....................................................................................................... 56 3.4 Experimental Details ........................................................................................ 57 iv Chapter 4: The Mechanism of Carboxylative Cyclization of Propargylamine by N- Heterocyclic Carbene Complexes of Au(1) 4.1 Background ..................................................................................................... 68 4.2 Results and Discussion .................................................................................... 73 4.3 Conclusion ....................................................................................................... 102 4.4 Experimental Details ........................................................................................ 102 Chapter 5: Ball Milling Reaction of Na2O and Na2O2 with N2O 5.1 Background .................................................................................................... 106 5.2 Results and Discussion .................................................................................... 108 5.3 Conclusion ....................................................................................................... 115 5.4 Experimental Details ........................................................................................ 116 References…………… ................................................................................................ 120 v List of Figures Figure 1.1. Projected growth in atmospheric CO2 fraction (left) and the projected increase in global surface temperature in the 21st century (right). ......................1 Figure 1.2 The total oxidation of N2O to NaNO3 using sodium peroxide and more N2O as oxidants is calculated to be favorable
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