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Louisiana State University LSU Digital Commons LSU Historical Dissertations and Theses Graduate School 1973 The Reactions of the Higher Oxidation States of Uranium and Molybdenum With Some Organic Heterocycles. Henry Jonathan Sherrill Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses Recommended Citation Sherrill, Henry Jonathan, "The Reactions of the Higher Oxidation States of Uranium and Molybdenum With Some Organic Heterocycles." (1973). LSU Historical Dissertations and Theses. 2570. https://digitalcommons.lsu.edu/gradschool_disstheses/2570 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]. 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Xerox University Microfilms 300 North Zeeb Road Ann Arbor, Michigan 48106 rI I 74-18,366 [; SHERRILL, Henry Jonathan, 1941- i I THE REACTIONS OF THE HIGHER OXIDATION STATES 1 | OF URANIUM AND MOLYBDENUM WITH SCME ORGANIC 1 HETEROCYCLES. I The Louisiana State University and Agricultural and Mechanical College, Ph.D., 1973 Chemistry, inorganic j f University Microfilms, A XEROX Company, Ann Arbor, Michigan k © 1974 HENRY JONATHAN SHERRILL ALL RIGHTS RESERVED THIS DISSERTATION HAS BEEN MICROFILMED EXACTLY AS RECEIVED. THE REACTIONS OF THE HIGHER OXIDATION STATES OF URANIUM AND MOLYBDENUM WITH SOME ORGANIC HETEROCYCLES 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 Henry Jonathan Sherrill B.S., Spring Hill College, I963 M.S., Auburn University, 1966 December, 1975 For Suzanne ACKNOWLEDGEMENT The writer wishes to express his deep appreciation to the director of this research, Professor Joel Selbin, for his inspiration, assistance, and friendship. The writer is also grateful for the patience and support of his wife, Suzanne. The help of Dr. Dave Durrett, Dr. G. R. Newkome, and Dr. Anita Bigger is also appreciated. Financial support from Louisiana State University-Baton Rouge through a National Defense Education Act Title IV Fellowship, a teaching assistantship, and a research assistantship through NSF funds is acknow­ ledged. 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 A ...............................acridine Bu..............................butyl CEE.............................cysteine ethylester dlanion CEEH. ........................cysteine ethylester monoanlon CEEHS...........................cysteine ethylester DACDEE......................... N ,N/-diacetylcystlne dlethylester DMAZ............................1 ,3-dlmethylalloxazlne DMIA............................3»10-dlme thy llsoalloxazlne EAMIA...........................3-ethy lace t oxy- 10-methy llsoalloxaz Ine Et............................. ethyl Me..............................methyl Ph............................. phenyl Fr............................. propyl PT............................. phenothiaz ine Py........ ..................... pyridine RTA............................ riboflavin tetraacetate RTB............................ riboflavin tetrabutyrate TCAC........................... trichloroaczylylchloride TMAZ........................... 1 ,3,7,8-tetramethylalloxazlne TMIA........................... 3 ,7,8,10- 1 e trame thy 1 is oal 1 oxaz ine iv TABLE OF CONTENTS PAGE ACKNOWLEDGEMENT............................................. ill LIST OF ABBREVIATIONS....................................... iv LIST OF TABLES.............................................. vil LIST OF FIGURES............................................. ix TABLE OF STRUCTURAL FORMULAS................................ xlll ABSTRACT.................................................... XV HISTORY..................................................... xvii PART I. THE REACTIONS OF URANIUM(v) WITH SOME ORGANIC HETEROCYCLES....................................... 1 CHAPTER I. INTRODUCTION..................................... ... 2 A. Survey of the Literature on Pentavalent Uranium... 2 B. Scope of the Present Research.................... k II. EXPERIMENTAL PROCEDURES.............................. 6 A. Technique....................................... 6 B. Materials....................................... 7 C. Reactions and Preparations of C o m p o u n d s 9 D. Analyses and Physical Measurements............... 32 III. THEORETICAL AND SPECTRAL STUDIES ON THE UOFg2" AND UOBr52“ SPECIES..................................... 36 A. Theory.................. 36 B. Results and Discussion of Theoretical and Spectral Studies............................ 32 IV. PHYSICAL-CHEMICAL STUDIES ON THE URANIUM COMPOUNDS 74 A. KqUFe*2HF....................................... 74 B. (pt)2UC16....................................... 79 C. AHaCl........................................... 83 D. The Alloxazlne and Isoalloxazlne Compounds with Uranium.................................... 86 V. SUGGESTIONS FOR FURTHER WORK......................... 104 v PAGE PART II. THE REACTIONS OP MOLYBDENUM( IV, V, VI) WITH SOME ORGANIC HETEROCYCLES............................... 106 CHAPTER VI.. INTRODUCTION......................................... 107 A. Survey of the Literature on MoIybdenum(IV, V, Vi).. 107 B. Scope of the Present Research..................... I3 I VII. EXPERIMENTAL PROCEDURES............... 134 A. Technique...................... 134 B. Materials........................................ 134 C. Reactions and Preparations of Compounds........... 134 D. Analyses and Physical Measurements................ 144 VIII. PHYSICAL-CHEMICAL STUDIES ON THE MOLYBDENUM COMPLEXES.. 145 A. PTMoOC14 and PTMoO£Cle............ 145 B. Thermal Studies.................................. 148 C. Spectral Studies ............ 159 IX. SUGGESTIONS POR FURTHER WORK......................... 178 REFERENCES.................................. 182 APPENDIX 1................................................... 199 VITA......................................................... £04 vl LIST OF TABLES TABLE PAGE I. Unsuccessful Attempts to Prepare Salts of UFe"...... 25 II. Variation of the Calculated Values (kK) of A and 0 as a Function of § for UFe ...................... U€> III. Variation of the Calculated Values (kK) of A and 6 as a Function of £ for UBre ..................... kj IV. The Electronic and Vibronlc Bands for (Et4^)^U0F5.... 53 V. The Electronic and Vibronlc Bands for (Et4N)^UOBr5... 61 VI. Molybdenum Halides................... 108 VII. Reactions of Molybdenum Halides..................... 110 VIII. Molybdenum Oxide Halides...................... 115 IX. Oxo Complexes of Molybdenum........ 117 X. Complexes with Organic Nitrogen Donors, Oxlmes, 'i and EDTA.......................................... 125 XI. Complexes with Organic Sulfur Donors................ 125 XII. Ear Parameters for Molybdenum Enzymes and Representative Complexes.......................... 128 X U I . Complexes with Cysteine and Related Ligands.......... I50 XIV. The Spectral Bands for the Molybdenum Complexes and the Appropriate Ligands.......... I65 XV. The Pertinent Infrared Bands for the Two Derivatives of Cysteine and Their Corresponding Complexes with Molybdenum........... ;.................

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