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Isolation of Soft Donor Complexes of D- and F-Block Metals

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Isolation of Soft Donor Complexes of D- and F-Block Metals ISOLATION OF SOFT DONOR COMPLEXES OF D- AND F-BLOCK METALS USING IONIC LIQUIDS by STEVEN PAUL KELLEY ROBIN D. ROGERS, COMMITTEE CHAIR DAVID E. NIKLES THOMAS P. VAID DAVID A. DIXON ANJA-VERENA MUDRING A DISSERTATION Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the Department of Chemistry in the Graduate School of The University of Alabama TUSCALOOSA, ALABAMA 2015 Copyright Steven Paul Kelley 2015 ALL RIGHTS RESERVED ABSTRACT Ionic liquids (ILs) are alternatives to conventional molecular liquids or high-melting salts which can be used to gain new insight into long-standing scientific questions. The ability to access a compositionally variable, purely ionic liquid environment in an IL is particularly significant in coordination chemistry, which often involves the manipulation of an ionic metal- ligand bond. This study aims to demonstrate the potential utility of ILs in coordination chemistry by using them to access unusual metal complexes with soft Lewis bases, especially those of f- elements. Such complexes are particularly important use in studying the nature of f-element chemical bonding and the interactions involved in their isolation, propagation through the environment, or distribution in living organisms. A number of strategies using ILs and systems derived from ILs are explored. In reactions of dicyanamide-containing ILs with uranyl salts, the use of an IL as a source of nitrogen-containing soft donor ligands led to the isolation of uranyl dicyanamide complexes through substitution of oxygen-donor ligands by IL anions. By reacting actinide nitrate hydrates with a nitrate-containing IL, anhydrous complexes were obtained which could be used as precursors for the formation of nitrogen-donor adducts. The permanent elimination of oxygen- containing anions from a metal salt was explored through reactions of an acidic azole with metal acetate salts, although this approach was found to be limited by side reactions. The use of a partially anionic sulfur ligand derived from an IL led to the formation of uranyl and neodymium sulfur-donor complexes. The scope of nitrogen-containing ligands which could be incorporated ii into an IL was expanded by demonstrating the use of combinations of acidic and basic azoles as liquids for nitrogen donor coordination chemistry. These platforms have considerable room for expansion beyond the metal complexes already isolated. Future studies will expand the range of soft donors incorporated in the IL beyond nitrogen. Combinations of these strategies will also be explored with the aim of producing entirely soft-donor ligated complexes from readily available starting materials. iii LIST OF ABBREVIATIONS AND SYMBOLS (O)2 Two oxide ligands (OH2) Aqua ligand + [(C4CN)(C2CN)Im] 1-(4-Cyanobutyl)-3-(2-cyanoethyl)imidazolium - [AlCl4] Tetrachloroaluminate anion [C2C2Im][OAc] 1,3-Diethylimidazolium acetate + [C2mim] 1-Ethyl-3-methylimidazolium + [C4mpyrr] N-Butyl-N-methylpyrrolidinium + [Cnmim] 1-Alkyl-3-methylimidazolium cation 3- [LnCl6] Hexachlorolanthanate - [N(CN)2] Dicyanamide + [NH4] Ammonium cation - [NO3] Nitrate - [NTf2] Bis(trifluoromethane)sulfonylamide [OAc]- Acetate 2- [Pu(NO3)6] Hexanitratoplutonate 2- [PuCl6] Hexachloroplutonate 2- [SO4] Sulfate anion 2+ [UO2] Uranyl cation 1,2,4-TAZ 1,2,4-Triazole 1-mim 1-Methylimidazole 2θ X-ray diffraction angle iv 4,4’-bipy 4,4’-Bipyridyl 4,5-DCNIm 4,5-Dicyanoimidazole 5-AcAT 5-Acetamidyltetrazole 5-AT 5-Aminotetrazole a Crystallographic a axis Reacts to form Å Angstrom Ag Silver An Actinide Ar Argon ATR Attenuated total reflectance b Crystallographic b axis Ba(N(CN)2)2 Barium dicyanamide Br Bromide BTPhen 2,9-Bis(1,2,4-triazin-3-yl)-1,10-phenanthroline C Carbon c Crystallographic c axis C=O C-O double bond C≡N C-N triple bond C2C2ImT 1,3-Diethylimidazole-2-thione CCD Charge-coupled device CCDC Cambridge Crystallographic Data Center Ce Cerium Cl Chlorine Cl- Chloride v cm-1 Wavenumber CMPO Octyl(phenyl)-N,N-diisobutylcarbomoylmethylphosphine oxide CO Carbon monoxide CrCl3 Chromium(III) chloride CSD Cambridge Structural Database Cu Copper Cu(NO3)2·2.5H2O Copper(II) nitrate hemipentahydrate Cu-Kα Copper K-alpha CuO Copper(II) oxide DI Deionized DSC Differential Scanning Calorimetry DTPA Diethylenetriaminepentaacetic acid eq. Equivalent Eq. Equation Eu Europium F Fluorine F2 Squared structure factor magnitude FT Fourier transform g Gram h Hour H2O Water H2SO4 Sulfuric acid H-Az Acidic azole Hg Mercury HgCl2 Mercury(II) chloride vi H-Im Imidazole HOAc Acetic acid I Iodine Icalc Calculated structure factor IL Ionic Liquid Iobs Observed structure factor IR Infrared kJ Kilojoule L Generic ligand Ln Lanthanide M Moles/liter M(Az)x Metal azolate M(OAc)x Metal acetate mCi MilliCurie Mg Milligram min Minute mL Milliliter mm Millimeter mmol Millimole Mo-Kα Molybdenum K-alpha mol Mole MΩ·cm Megaohm centimeter N Nitrogen N2 Dinitrogen Na Sodium vii NaN(CN)2 Sodium dicyanamide Nd Neodymium Nd(NO3)3·6H2O Neodymium nitrate hexahydrate NdCl3·6H2O Neodymium chloride hexahydrate N-donor Nitrogen donor Ni Nickel NMR Nuclear magnetic resonance Np Neptunium O Oxygen oC Degrees Celsius O-donor Oxygen donor ORTEP Oak Ridge Thermal Ellipsoid Plot Pb Lead Pb(OAc)2·3H2O Lead(II) acetate trihydrate Pd Palladium ppm Part per million Pu Plutonium PXRD Powder X-ray diffraction Rint Residual for merging equivalent X-ray diffraction reflections S Sulfur SCXRD Single crystal X-ray diffraction TALSPEAK Trivalent Actinide Lanthanide Separation by Phosphorous Reagent Extraction of Aqueous Komplexes Th Thorium Th(NO3)4·4H2O Thorium nitrate tetrahydrate THF Tetrahydrofuran viii TRUEX TransUranic Extraction U Uranium U=O Uranyl U-O multiple bond UO2(NO3)·6H2O Uranyl nitrate hexahydrate UO2(OAc)2·2H2O Uranyl acetate dihydrate UO2Cl2·3H2O Uranyl chloride trihydrate UO3 Uranium trioxide UV/Vis Ultraviolet/Visible Light wR2 Square of the weighted least squares residual XAFS X-ray absorption fine structure Z Formula units per unit cell Zn Zinc ZnO Zinc oxide α Crystallographic alpha angle or alpha position on a molecule β Crystallographic beta angle γ Crystallographic gamma angle η2 Eta-2 hapticity λmax Maximum absorption wavelength μ Linear X-ray absorption coefficient σ Standard uncertainty -NH2 Amine functional group ix ACKNOWLEDGMENTS I would first like to thank my research advisor, Prof. Robin Rogers, for the opportunity to do some truly exciting research in his group. I thank my committee members, Profs. Thomas Vaid, David Nikles, David Dixon, and Anja Mudring, for the support and guidance I have received from them especially as I have been concluding my time as a graduate student. I also thank all the faculty I have had the privilege to work with during my time as the Department X- ray facility manager at UA for the many opportunities they have given to broaden my chemistry horizons. I would like to thank all my current and former group members, especially my fellow grad students Leah and Chris, my former group members Marcin and David who helped get me started, and my current group members Paula Berton and Julia Shamshina for their unending support. I also want to thank some of my current and former classmates and colleagues from other with whom I’ve gotten to work over the years: Matt Hennig, Steven Raders, Edward Ellingsworth, Joe Meany, Deidra Gerlach, and probably too many more to list. I’d like to thank my wife Victoria Kelley on behalf of the whole group for her years uncredited help to everyone. Finally, I’d like to thank the U.S. Department of Energy NEUP program for their support and travel opportunities. I’d also like to thank the DOE for their support in giving me the opportunity to attend the Annual School on Neutron and X-Ray Scattering, Oak Ridge Associated Universities for the opportunity to attend the 63rd Lindau Meeting, and the UA College of Arts and Sciences for the opportunity to participate in the first 3 Minute Thesis competition. Lastly, I thank the Department of Chemistry for all their support. Roll Tide! x CONTENTS ABSTRACT ...........................................................................................................................ii LIST OF ABBREVIATIONS AND SYMBOLS ..................................................................iv ACKNOWLEDGMENTS .....................................................................................................x LIST OF TABLES .................................................................................................................xvi LIST OF FIGURES ...............................................................................................................xvii CHAPTER 1: INTRODUCTION .........................................................................................1 1.1: Coordination chemistry in ionic liquids...................................................................1 1.2: Coordination chemistry of f-elements with soft donor ligands ...............................4 1.3: Research plan and purpose of project ......................................................................9 1.4: References ................................................................................................................12 CHAPTER 2: ISOLATION OF URANYL DICYANAMIDE COMPLEXES FROM N-DONOR IONIC LIQUIDS ........................................................................18 2.1: Introduction ..............................................................................................................18 2.2: Experimental ............................................................................................................22
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