And Related Species. David Glen Durrett Louisiana State University and Agricultural & Mechanical College
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Louisiana State University LSU Digital Commons LSU Historical Dissertations and Theses Graduate School 1972 Theoretical, Physical, and Chemical Studies of Oxouranium(v) and Related Species. David Glen Durrett Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses Recommended Citation Durrett, David Glen, "Theoretical, Physical, and Chemical Studies of Oxouranium(v) and Related Species." (1972). LSU Historical Dissertations and Theses. 2279. https://digitalcommons.lsu.edu/gradschool_disstheses/2279 This Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons. It has been accepted for inclusion in LSU Historical Dissertations and Theses by an authorized administrator of LSU Digital Commons. For more information, please contact [email protected]. INFORMATION TO USERS This dissertation was produced from a microfilm copy of the original document. 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Michigan 48106 A Xerox Education Company I I 73-2952 DURREIT, David Glen, 19^2- THBORETICAL, PHYSICAL, AND CHEMICAL STUDIES OF OXOURANIUM(V ) AND RELATED SPECIES. The Louisiana State University and Agricultural and Mechanical College, Ph.D., 1972 Chemistry, inorganic University Microfilms, A XEROX Company, Ann Arbor, Michigan THEORETICAL, PHYSICAL, AND CHEMICAL STUDIES OF OXOURANIUM(V) AND RELATED SPECIES A Dissertation Submitted to the Graduate Faculty of the Louisiana State University and Agricultural and Mechanical College in partial fulfillment of the requirements for the degree of Doctor of Philosophy in The Department of Chemistry by David Glen Durrett B.S., University of Southwestern Louisiana, 1964 Th.M., New Orleans Baptist Theological Seminary, I968 August, 1972 PLEASE NOTE: Some pages may have indistinct print. Filmed as received. University Microfilms, A Xerox Education Company To Dianne ACKNOWLEDGMENT The writer wishes to express his appreciation to the director of this research, Professor Joel Selbin, for his encouragement, guidance, and assistance. The writer is also grateful for the patience and sup port of his wife, Dianne. The help of Mr. Jon Sherrill and Dr. G. R. Newkome is also appreciated. Financial support from Louisiana State University through a National Defense Education Act Title IV Fellowship and a Dissertation Year Fellowship is acknowledged. The writer also acknowledges the financial assistance received from the Dr. Charles E. Coates Memorial Fund of the Louisiana State University Foundation, donated by George H. Coates, for the publication of this Dissertation. iii LIST OF ABBREVIATIONS BP................................benzo [a] phenaz ine Bu................................butyl DBP...............................dibenzo [a, c] phenaz ine dipy..............................2 ,2 '-bipyridyl DMA. ......................... ,N,N-dimethylacetamide DMF...............................N,N-dimethylformamide DMSO..............................dimethylsulfoxide dpm...............................2 ,2 ,6 ,6-tetramethyl-3 ,5-heptanedione DPyQ..............................2,3“di(2-pyridyl)quinoxaline EBDPP.............................ethy lenebis ( d ipheny lphosph ine ) EPA...............................ethyl ether-isopentane-ethanol mixture Et................................ethyl HMPA..............................hexamethylphosphoramide, [(CH3) aNjsPO HT .......................... tropolone MB................................methylene blue Me................................methyl oxine.............................8-quinolinolate anion oxine H ................ ...........8-quinolinol P .................................phenaz ine Ph................................phenyl o- phen............................o- phenanthrol ine Pr................................propyl ^-Pr..............................isopropyl PrenC03 ...........................propylene carbonate iv PT..................... ...........phenothiazine Py................................ pyridine Qi................................ quinoline .i-Qi.............................. isoquinoline T ................................. tropolonate anion TGAC.............................. trichloroacrylyl chloride THF............................... tetrahydrofuran TABLE OF CONTENTS Page ACKNOWLEDGMENT.................................................. lit LIST OF ABBREVIATIONS . iv LIST OF TABLES............................................... viii LIST OF FIGURES.............................................. ix TABLE OF STRUCTURAL FORMULAS................................. xi ABSTRACT..................................................... xiii HISTORY...................................................... xv CHAPTER I. INTRODUCTION.......................................... 1 A. Stability and Importance of Pentavalent Uranium.... 1 B. Survey of the Literature on Pentavalent Uranium.... 1 C. Scope of the Present Research.......... 46 II. EXPERIMENTAL PROCEDURES............................... 48 A. Technique................. 48 B. Materials......................................... 49 C. Reactions and Preparations of Compounds........... 52 D. Analyses and Physical Measurements................ 91 III. THEORETICAL, SPECTRAL, AND CHEMICAL STUDIES OF THE UOCls2" SPECIES................................ 96 A. Theory............................................ 96 B. Results and Discussion of Spectral Studies........ 102 C. The Ultraviolet Spectrum.......................... 123 D. Other Physical-Chemical Studies of the U0C15^ Species................................... 12? IV. FREE RADICAL FORMATION BY PENTAVALENT METAL IONS....... 133 A. The UOCls^" Adducts............................... 133 B. The Dihydrophenazlne Cation Radical............... 150 C. Other Radicals Formed by U(v)............... 163 D. Reactions of (Et4N)2U0Cl5 with Other Ligands...... 167 E. Reactions of Phenazine with Mo(V) Compounds....... 168 V. SOME ADDITIONAL ASPECTS OF THE CHEMISTRY OF U(IV), U(V) AND Mo(v)................................. 1?2 VI. SUGGESTIONS FOR FURTHER WORK.......................... 1?4 vi LIST OF REFERENCES....................................... 181 VITA..................................................... 19b vii LIST OF TABLES Table Page I. Recent Magnetic Data for Uranium(v) Compounds......... 23 II. EPR Data for Uranium(v) Compounds..................... 27 III. Vibrational Band Assignments for UX6 Complexes....... 30 IV. Uranium-Oxygen Vibrational Frequencies (in cm"1) for (Et4N)2U0X5 Compounds............................ 33 V. Vibrational Frequencies (cm-1) for UX6 Salts from Vibronic Components of the Ty* T7 Transition... hO VI. Unsuccessful Attempts to Prepare Metal Salts of U0C152'.............................................. 63 VII. Variation of Calculated Values (kK) of A and 9 as a Function of £ ........................................ 100 VIII. The Electronic and Vibronic Bands Found for (Et4N)2- U0C15................................................ 105 IX. The r? *+ Ty* Transition in Various U(v) Compounds 117 X. The Bands Observed for (Et^JjgUOCls in the Region of Laporte-Allowed Transitions....................... 123 XI. Absorption Bands (cm-1) of the (Et4M)2U0Cl5 Adducts and Ligands in the NaCl and Csl Regions.............. 1^0 XII. Free Radicals Formed by ( Et^aUOXs (X * Cl, Br) 16U viii LIST OF FIGURES Figure Page 1. Energy Levels for a ^f1 Electron Split by Spin- Orblt Coupling and an Octahedral Crystal Field...... 35 2. The Effects of Octahedral Crystal Field Strength on the Energy Levels of a 5f1 System............... 36 3 . Energy Levels for a 5fa Electron Split by Spin- Orbit Coupling and an Axial Crystal Field........... L4 U. Apparatus for Preparation of UC15 *TCAC.............. 33 5 . The Electronic Spectrum of