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Part I. Electrostatic and Steric Effects on the Acidity and Stability of Metal Complexes of a Series of Malonic Acids; Part Ii

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Part I. Electrostatic and Steric Effects on the Acidity and Stability of Metal Complexes of a Series of Malonic Acids; Part Ii This dissertation has been microfilmed exactly as received 68-15,331 HILTON, Ashley Stewart, 1940- PART I. ELECTROSTATIC AND STERIC EFFECTS ON THE ACIDITY AND STABILITY OF METAL COMPLEXES OF A SERIES OF MALONIC ACIDS; PART II. INTERACTION OF DIAMINES WITH GLYOXYLIC ACID AND EFFECT OF METAL IONS UPON IT. The Ohio State University, Ph.D., 1968 Chemistry, general University Microfilms, Inc., Ann Arbor, Michigan © _ Ashlev Stewart Hilton 1969 ALL RIGHTS RESERVED PART I . ELECTROSTATIC AND STERIC EFFECTS ON THE ACIDITY AND STABILITY OF METAL COMPLEXES OF A SERIES OF MALONIC ACIDSj PART I I . INTERACTION OF DIAMINES WITH GLYOXYLIC ACID AND EFFECT OF METAL IONS UPON IT DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Ashley Stewart Hilton, B.S. ****** The Ohio State University 1968 Approved by Ad Mst Department of Chemistry ACKNOWLEDGMENTS The author wishes to express his appreciation to Dr. Daniel L. Leussing for his professional guidance and encouragement throughout the course of this work. Gratitude is expressed to the National Science Foundation, The Ohio State University Grant-in-Aid program, and this Chem­ istry Department for financial aid while attending Graduate School. I am especially grateful to my wife, Sharon, for her constant encouragement during this work and for undertaking the enormous task of typing this dissertation. VITA April 28, 1940 Born - Saint Marys, Pennsylvania 1962 .................... B.S., The Pennsylvania State University, University Park, Pennsylvania 1962-1967. Teaching and Research Assistant, Depart­ ment of Chemistry, The Ohio State University, Columbus, Ohio 1967 .................... Aerospace Research Laboratory, Wright- Patterson Air Force Base, Ohio PUBLICATIONS None FIELDS OF STUDY Major Fieldi Chemistry Studies in Laboratory Management of Research and Development. Lt. Colonel L. E, Winebrenner (Ret.) iii TABLE OF CONTENTS Page ACKNOWLEDGMENTS..................................................................................... i i VITA..........................................................................................................................i i i LIST OF TABLES.......................................................................................... vi LIST OF FIGURES...........................................................................................v ii PART I. ELECTROSTATIC AND STERIC EFFECTS ON THE ACIDITY AND STABILITY OF METAL COMPLEXES OF A SERIES OF MALONIC ACIDS Chapter I. INTRODUCTION................................................ ...................... 2 A. Research Objectives , . ...................... 3 B. Theoretical Background . ........................... 6 II. EXPERIMENTAL METHODS....................................................... 12 A, Chemicals......................................................... 12 B. Experimental Methods ................................ 20 III. TREATMENT OF DATA............................................................ 24 IV. RESULTS AND DISCUSSION.................................................. 30 PART II. INTERACTION OF DIAMINES WITH GLYOXYLIC ACID AND EFFECT OF METAL IONS UPON IT I. INTRODUCTION........................................................................... 43 A. Review of Preceding Work ........ 44 B. Introduction to Research Problem .... 52 II. EXPERIMENTAL METHODS....................................................... 58 A. Chemicals......................................................... 58 B. Experimental Methods ................................ 64 iv TABLE OF CONTENTS (Cont.) Chapter Page III. TREATMENT OF DATA.......................................................... 68 IV. RESULTS AND DISCUSSION................................................ 80 APPENDIXES A. Acid Dissociation Data for Malonic Acid , . 139 B. Data for Zn and Cd Complexes of the Malonic A c i d s ...............................................................................................145 C. Data for Simple C o n s ta n ts .............................................152 D. Data for Diamine Dihydrochloride-Glyoxalate S y s te m s ..........................................................................................164 E. Data for Diamine Dihydrochloride-Glyoxalate- Metal S y ste m s ...........................................................................171 F. Distribution Curves of Tetrameen and Glyoxalate Species in the Tetrameen- Glyoxalate System ........................................................... 180 G. Distribution Curves of En and Glyoxalate Species in the En-Glyoxalate System .... 191 H. Distribution Curves of Zn(II) and Ni(II) in the Metal-Tetrameen-Glyoxalate System . 202 I. Distribution Curves of Zn(ll) and Ni(II) in the Metal-En-Glyoxalate System ....... 211 J, Structures of Malonic A c i d s ........................................220 LIST OF REFERENCES....................................................................................222 v LIST OF TABLES Table Page Part I 1. Constants and Related D a ta ...................... 31 2. Nuclear Magnetic Resonance D a ta ............ 36 Part II 3. Definitions of C o n s ta n ts ........................... 72 4. Logarithms of the Constants for Glyoxylic Acid, Ethylenediamine-2 HC1 and c.c.c’.c'- Tetramethylethylenediamine-2 HCI .................... 81 5. Logarithms of the Constants Describing the Diamine-Glyoxalate Systems a t 25°C with Ionic Strength ....................................... 105 6. Logarithms of Constants Describing the Metal- Diamine-Glyoxalate Systems at 25°C with Ionic Strength , ....................................................... 130 vi LIST OF FIGURES Figure Page Part I 1. Maleic and Fumaric Acid Structures .... 10 2. c is - and trans-Caronic Acid Structures . 10 3. Preparation of Malonic Acids by Hydrolysis of the Diethyl Ester .................................... 14 4. Preparation of 1,1-Cyclopropanedicarboxylic Acid ...................................................................................... 15 5. Gas Chromatogram of Crude Diethyl 1,1- Cyclopropanedicarboxylate ......................................... 17 6. Gas Chromatogram of Crude Diethyl 1,1- Cyclobutanedicarboxylate ......................................... 18 Part II 7. Typical Transamination in a Model System . 44 8. Mechanism Postulated for Model Transamination System s ..................................................................................... 46 9. Definition of Overall Formation Constants O i j ) ........................................................................................... 50 10. Frotonated Schiff-Base Complex in the Fyridoxal-Glycinate System .................................... 53 11. Cyclic Structure Formed From Reaction of Acetone With a Series of M(II) C-Substituted Ethylenediamines .................................................. 53 12. Imidazoline Formation From Reaction of Substituted Ethylenediamines With Carboxylie Acids ..................................................................................... 55 vii LIST OF FIGURES (Cont.) Figure Page 13. Imidazolidine Formation From Reaction of 56 Substituted Ethylenediamines With Aldehydes 14. Synthesis of Na-2-Nitropropane ................................ 59 15. Synthesis of 2-iodo-2-Nitropropane ...................... 59 16. Synthesis of 2,3-dinitro-2,3-Dimethylbutane . 61 17. Synthesis of c(c,c' , c'-Tetramethylethylene- diamine'2 HC1 ...................................................................... 61 18. Structures of the Protonated Complexes . 79 19. Preliminary Titration Curves for the Tetrameen-Glyoxalate System ........................................ 85 20. Preliminary Titration Curves for the En- Glyoxalate System ................................................................. 87 21. NMR Spectra of Tetrameen*2 HC1 Versus Percent Neutralization ...................................................................... 91 22. NMR Spectra of Na Glyoxalate + Tetrameen*2 HC1 Versus Percent Neutralization ................................... 93 23. NMR Spectra of Na Glyoxalate + Tetrameen*2 HC1 Versus p H ..................................................................................... 96 24. NMR Spectra of Na Glyoxalate + en*2 HC1 Versus p H .................................................................................................... 98 25. Proposed Diamine-Glyoxalate Reaction Products 101 26. Formation of an Imidazoline From Reaction of Glyoxalate With A Diamine ....................................................102 27. Formation of an Imidazolidine From Reaction of Glyoxalate With A D iam ine ..........................................102 28. General Structure of an Imidazolidine-2- Car boxy la t e .......................................................................................104 29. Curve-Fit for F irst Plateau Region of the Titration Curves for the CjCi C'^c 1- Tetramethylethylenediamine•2 HC1 and Glyoxylic Acid Mixtures .................................................. 108 v m* * * LIST OF FIGURES (Cont.) Figure Page 30. Curve-Fit for Second Plateau Region of the T itration Curves for the 0 , 0 , 0 ' ,c '- Tetramethylethylenediamine*2 HC1 and Glyoxylic Acid M ixtures ................................................. 110 31. Curve-Fit for the First Plateau Region of the T itration Curves for the Ethylenediamine*2 HC1 and Glyoxylic Acid M ixtures .....................................112 32, Curve-Fit for the Second Plateau Region of
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