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Preparations, Solution Composition, and Reactions of Complex Metal Hydrides and Ate Complexes of Zinc, Aluminum, and Copper a Th

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PREPARATIONS, SOLUTION COMPOSITION, AND REACTIONS OF COMPLEX METAL HYDRIDES AND ATE COMPLEXES OF ZINC, ALUMINUM, AND COPPER A THESIS Presented to The Faculty of the Division of Graduate Studies By John Joseph Watkins In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the School of Chemistry Georgia Institute of Technology April, 1977 PREPARATIONS, SOLUTION COMPOSITION, AND REACTIONS OF COMPLEX METAL HYDRIDES AND ATE COMPLEXES OF ZINC, ALUMINUM, AND COPPER Approved: Erlin^rbrovenstein, Jr., Chairman H. 0. House E. C. Ashby Date approved by Chairman £~^3c>l~l~f ii ACKNOWLEDGMENTS Many individuals and organizations have contributed to the successful completion of this thesis. The following acknowledgments are not complete, but I hope I have expressed my gratitude to the people and organizations upon whom I depended the most. The School of Chemistry supported my first three years of work by the award of an NSF fellowship. My last year of work was generously supported by the St. Regis Paper Company, who graciously gave me leave of absence with salary so that the requirements for this thesis could be completed. This stipend and tuition support of my work freed me to concentrate on research without the financial difficulties encountered by many graduate students. All the faculty and staff of the School of Chemistry supported my research. I particularly would like to recognize Professor W. M. Spicer, Professor J. A. Bertrand, Professor C. L. Liotta, Mr. Gerald O'Brien, and Mr. D. E. Lillie. Post-doctoral assistants and fellow graduate students who contributed to my experience at the Georgia Insti­ tute of Technology include Dr. G. A. Marano, Dr. R. D. Schwartz, Dr. J. T. Leammle, Dr. J. H. Smith, Dr. G. E. Parris, and Mr. J. P. Oliver. I would especially like to recognize Mr. Roy L. Miller, Dr. Ivar H. Stockel, and Dr. R. D. Raymond of the St. Regis Paper Company. Without the special encouragement provided by these three people I may never have returned to finish this thesis. iii Professor E. C. Ashby suggested the areas of study covered in this thesis and advised on the research as it progressed. Professor Ashby allowed me considerable freedom during the course of these studies to satisfy my curiosity regarding observations not directly linked to my thesis. I thank Professor Erling Grovenstein, Jr. and Professor H. 0. House for reading my thesis and making helpful comments. My mother and father, Gladys C. and James L. Watkins, provided me with the opportunity and incentive to attend high school and college. Any success I have had or will have is based upon the foundation they laid. My wife, Alice, and our three daughters, Lisa, Karen, and Susan, should be acknowledged for the patience, love, and understanding they provided during the preparation of this thesis. iv TABLE OF CONTENTS Page AC KNO WLEDGMENTS i i LIST OF TABLES viii LIST OF ILLUSTRATIONS xi SUMMARY xvi Chapter PART I The Synthesis and Characterization of Complex Metal Hydrides Involving Zinc and the Alkali Metals (Li, Na, and K) I. INTRODUCTION 2 II. EXPERIMENTAL 6 Apparatus 6 Analytical 8 Materials 8 Procedure 10 Reactions Involving (s-C^Hg^Zn Reactions Involving (CHo) 2Zn and LiH Reactions of KH with ZnCl2 in THF Reaction of KC1 with ZnCl2 in 1:1 Molar Ratio in THF Reaction of AlHo with the Filtrate from the Reaction of KC1 with ZnCl^ in THF Reaction of NaH with ZnCl2 in 1:1 Molar Ratio in THF Reaction of LiH with ZnBr2 in 2:1 Molar Ratio in THF Reaction of NaH with Znl2 in 2;1 Molar Ratio in THF Reactions Involving (CH^^Zn with CH^Li Reactions Involving (CH^^Zn with KH Reactions Involving (CH^)2Zn with NaH III. RESULTS AND DISCUSSION 35 Li2ZnH^ 35 V TABLE OF CONTENTS (Continued) Chapter Page Li3ZnH5 40 LiZnH3 41 LiZnH5 and LiZn3Hy 44 KZn(CH3)2H and KZn2(CH3)4H 44 KZn2H5 45 KZn3H? 51 KZnH3 51 NaZnH3 53 NaZn2H5 55 Reaction of Alkali Metal Hydrides with Zinc Halides in Tetrahydrofuran 56 LITERATURE CITED 64 PART II A Study Concerning the Existence of Complexes Between LiAlH^ and A1H3 in Ether Solvents and in the Solid State I. INTRODUCTION 67 II. EXPERIMENTAL 69 Apparatus 69 Analytical 69 Materials ?0 Procedure 70 Reaction of LiAlH^ and A1H4 in 1:1, 1:2, 1:3, and 1:4 Molar Ratio in Diethyl Ether Reaction of LiAlH^ and AlHo in 1:1, 1:2, 1:3, and 1:4 Molar Ratio in THF Reaction of LiH and A1H3 in 1:4 Molar Ratio in Diethyl Ether Reaction of LiAlH^ with BeCl2 in 4:1 Molar Ratio in Diethyl Ether. Formation of "LiAl2Hy" Reaction of LiAlH^ with BeCl2 in 2:1 Molar Ratio in Diethyl Ether Reaction of LiAlH^ with BeCl2 in 3:1 Molar Ratio. Formation of "LiAl3H^n" III. RESULTS AND DISCUSSION 73 IV. CONCLUSIONS 98 vi TABLE OF CONTENTS (Continued) Chapter Page LITERATURE CITED 100 PART III A Study Concerning the Nature of Alkyl-Hydrido Group Exchange Between Zinc and Aluminum in the Reactions of MZnx(CH3)2xH with Alane and MAIH^ with (CH3)2Zn (M = Li, Na, or K) I. INTRODUCTION 102 II. EXPERIMENTAL 105 Apparatus 105 Analytical 105 Materials 106 Procedure ..... 107 Reaction of AlH^ with LiZn(CHo)2H in Tetrahydrofuran Reaction of A1H with LiZn2(CH„),H in THF Reaction of AlH^ with LiZn \CB.J Am, in THF Reaction of AIH3 with LiZn2(CH374AIH4 in THF Reaction of LiAlH, with LiZn(CHo)2A1H, in THF Reactions of LiAlH^ with LiZn2(CH^AITL; in THF Reactions of LiAlH, with (CH3)2Zn in THF at Molar Ratios of 1:1, 2:3, and 1:2 Reactions of (CH3)2Zn with LiAlH^ in THF at Molar Ratios of 1:1, 3:2, and 2:1 Infrared Spectral Study of the Reaction of LiAlH^ with (CH3)2Zn in Diethyl Ether Redistribution of LiAlH^ and LiAl(CH3)^ Reactions where (CH3)2Zn Is Added to LiAlH^ in Diethyl Ether Reactions where LiAlH^ Is Added to (CH3)2Zn in Diethyl Ether Reaction of LiZn(CH3)2A1H^ with LiAlH^ in Diethyl Ether Reaction where LiAlH, Is Added to a Dilute Solution of (CH3)2Zn in 1:1 Ratio Reaction of NaZn(CH3)2H with AlHo in THF Reaction of NaZn2(CH3)^H with A1H3 in Tetrahydrofuran Infrared Study of the Reaction of NaAlH^ with (CH3)2Zn in THF Reaction of NaAlH^ with (CH3)2Zn in a 1:1 Molar Ratio Reaction of A1H3 with (CH3)2Zn in THF Reaction of ZnH2 with NaAl(CH3)2H2 in THF vii TABLE OF CONTENTS (Concluded) Chapter Page Preparation of KAIH^ Reaction of KZn(CH3)2H with A1H3 in THF Reaction of KAIH^ with (CH3)2Zn in THF in 1:1 Molar Ratio Reaction of KAIH^ with (CH3)2Zn in THF in a 1:2 Molar Ratio Reaction of KZn2(CH3)4H with A1H3 in THF at Molar Ratios of 2:1, 1:1, and 1:2 III. RESULTS AND DISCUSSION 125 IV. CONCLUSIONS 186 LITERATURE CITED 219 PART IV The Composition of Lithium Methylcuprates in Etheral Solvents I. INTRODUCTION 222 II. EXPERIMENTAL. 224 Apparatus ....... 224 Analytical 224 Materials 225 Procedure 227 Preparation of Cuprates General Reactions with 4-tert-Butylcyclohexanone Molecular Weight Measurements Interpretation of Exchange Mechanisms for NMR Data III. RESULTS AND DISCUSSION 232 IV. CONCLUSIONS 263 LITERATURE CITED 264 VITA 266 viii LIST OF TABLES Table Page PART I 1. X-Ray Powder Patterns for Complex Metal Zinc Hydrides of Lithium 12 2. X-Ray Powder Patterns of Solids from the Reaction of Alkali Metal Hydrides with ZnCl2 17 3. X-Ray Powder Patterns of Solids from the Reaction of Alkali Metal Hydrides with ZnBr2 and Znl2 23 4. X-Ray Powder Patterns for Complex Metal Zinc Hydrides of Potassium 27 5. X-Ray Powder Patterns for Complex Metal Zinc Hydrides of Sodium 32 PART II 1. Elemental Analysis of Mixtures of LiAlH^ and AlH^ in 1:1, 1:2, 1:3, and 1:4 Ratio in Diethyl Ether 77 2. X-Ray Powder Diffraction Patterns of the Solid Products Obtained in the Reactions of LiAlH^ with AlH^ in Diethyl Ether 78 3. X-Ray Powder Diffraction Patterns of "LiA^Hy" and "LiAl4H13" 93 PART III 1. Infrared Spectral Bands for (CH3)2Zn, A1H3, LiZn- (CH3)2H, LiZn2(CH3)4H, LiZn(CH3)2A1H,, and LiZn0(CH0)/AlH. in ?HF 127 2 3 4 4 2. Chemical Shifts for Methyl Groups in (CH3)2Zn, LiZn(CH3)2H, LiZn2(CH3)4H, LiZn(CH3)2A1H4, and LiZn2(CH3)4AlH4 in THF 134 ix LIST OF TABLES (Continued) Table Pa§e 3. Infrared Spectra of (CH3)2Zn, LiAlH4, LiZn- (CH3)2A1H4, LiZn2(CH3)4AlH4, and the Products Obtained by Mixing LiAlH4 and (CH3)2Zn in THF 140 4. Chemical Shifts for LiZn(CH3)2AIH4 and LiZn2~ (CH3)2A1H4 at Various Concentrations in THF 147 5. Chemical Shifts for LiZn(CH3)2AIH4 and LiZn2- (CH3)4A1H4 at Various Temperatures in THF 151 6. Equilibrium Constants at Various Temperatures for A1I S the Reaction LiZr(CH3) 2 V = LiZr(CH3) 2A1H4 + S in Tetrahydrofuran. 153 7. Equilibrium Constants at Various Temperatures for the Reaction LiZn2(CH3)4AlH4-S = LiZn2 (CH^Al^ + S in Tetrahydrofuran 155 8. Products Obtained from Various Reactions Between LiAlH4 and (CH3)2Zn in Diethyl Ether 160 PART IV 1. Chemical Shifts for the System CH3Li-CH3Cu in Dimethyl Ether 234 2. Chemical Shifts for the System CH3Li-CH3Cu in Tetrahydrofuran 236 3. Chemical Shifts for the System CH3Li-CH3Cu in Diethyl Ether 238 4. Chemical Shifts for the System CH3Li-CH3Cu»P(n-Bu)3 in Diethyl Ether 240 5.
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    University of Massachusetts Amherst ScholarWorks@UMass Amherst Doctoral Dissertations Dissertations and Theses November 2017 POLYORGANOSILOXANES: MOLECULAR NANOPARTICLES, NANOCOMPOSITES AND INTERFACES Daniel H. Flagg University of Massachusetts Amherst Follow this and additional works at: https://scholarworks.umass.edu/dissertations_2 Part of the Materials Chemistry Commons, Polymer and Organic Materials Commons, and the Polymer Chemistry Commons Recommended Citation Flagg, Daniel H., "POLYORGANOSILOXANES: MOLECULAR NANOPARTICLES, NANOCOMPOSITES AND INTERFACES" (2017). Doctoral Dissertations. 1080. https://doi.org/10.7275/10575940.0 https://scholarworks.umass.edu/dissertations_2/1080 This Open Access Dissertation is brought to you for free and open access by the Dissertations and Theses at ScholarWorks@UMass Amherst. It has been accepted for inclusion in Doctoral Dissertations by an authorized administrator of ScholarWorks@UMass Amherst. For more information, please contact [email protected]. POLYORGANOSILOXANES: MOLECULAR NANOPARTICLES, NANOCOMPOSITES AND INTERFACES A Dissertation Presented by Daniel H. Flagg Submitted to the Graduate School of the University of Massachusetts in partial fulfillment of the degree requirements for the degree of DOCTOR OF PHILOSOPHY September 2017 Polymer Science and Engineering © Copyright by Daniel H. Flagg 2017 All Rights Reserved POLYORGANOSILOXANES: MOLECULAR NANOPARTICLES, NANOCOMPOSITES AND INTERFACES A Dissertation Presented by Daniel H. Flagg Approved as to style and content by: Thomas J. McCarthy, Chair E. Bryan Coughlin, Member John Klier, Member E. Bryan Coughlin, Head, PS&E To John Null ACKNOWLEDGEMENTS There are countless individuals that I need to thank and acknowledge for getting me to where I am today. I could not have done it alone and would be a much different person if it were not for the support of my advisors, friends and family.