ALTERNATIVE SYNTHETIC METHODOLOGIES FOR THE SYNTHESIS OF ORGANOSILICON COMPOUNDS by PLOUSIA E. VASSILARAS Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy Thesis Advisor: Dr. Malcolm E. Kenney Department of Chemistry CASE WESTERN RESERVE UNIVERSITY August, 2011 CASE WESTERN RESERVE UNIVERSITY SCHOOL OF GRADUATE STUDIES We hereby approve the thesis/dissertation Plousia Vassilaras_____________ ___ candidate for the Ph.D. degree *. (signed) John Protasiewicz ___________ __ (chair of the committee) _________ Irene Lee_______________________________ Eve. F. Fabrizio___________________________ John Stuehr_______________________________ Malcolm E. Kenney________________________ (date) ______7-5-2011_________________ *We also certify that written approval has been obtained for any proprietary material contained therein. Dedicated to my parents Sofia and Elia and my brothers Dimitri, George and Yianni for always being next to me. Table of Contents page LIST OF TABLES ix LIST OF FIGURES xiii LIST OF SCHEMES xvi LIST OF SYMBOLS AND ABBREVIATIONS xviii ACKNOWLEDGMENTS xix ABSTRACT xx CHAPTER 1. INTRODUCTION TO THE SYNTHESIS OF SiCl4 AND 1 CHLOROSILANES Silicon 2 Uses of Silicon 4 Silicon Tetrachloride 5 Uses of Silicon Tetrachloride 8 Objectives 9 CHAPTER 2. PREPARATION AND CHARACTERIZATION FOR THE 10 SYNTHESIS OF SiCl4 AND CHLOROSILANES Reagents and Solvents 11 Instruments and Apparatus 11 i 29Si Nuclear Magnetic Resonance Spectroscopy 11 Processing Methods 11 CHAPTER 3. SYNTHETIC PROCEDURES FOR THE SYNTHESIS OF 12 SiCl4 AND CHLOROSILANES Currell’s Approach Experiments Attempts to Reproduce Reported Pyridine HCl-Catalyzed Syntheses 13 of Silicon Tetrachloride from Tetraalkoxysilanes and Thionyl Chloride Exploratory Experiments Uncatalyzed Synthesis of Silicon Tetrachloride from Tetramethoxysilane and 15 Chlorinating Agents Variously Catalyzed Syntheses of Silicon Tetrachloride from 16 Tetramethoxysilane and Chlorinating Agents Detailed Experiments Catalyzed Alkoxysilane-Thionyl Chloride Investigations DMF-Catalyzed Synthesis of Methylchlorosilanes from Methylmethoxysilanes 18 and Thionyl Chloride DMF-Catalyzed Synthesis of Methylchlorosilanes from Methylethoxysilanes 21 and Thionyl Chloride DMF-Catalyzed Synthesis of Ethylchlorosilanes from Ethylalkoxysilanes 22 and Thionyl Chloride DMF-Catalyzed Synthesis of Silicon Tetrachloride from Tetramethoxysilane 23 and Thionyl Chloride ii Variously Catalyzed Synthesis of Silicon Tetrachloride from Tetramethoxysilane 27 and Thionyl Chloride DMF-Catalyzed Synthesis of Silicon Tetrachloride from Tetramethoxysilane 30 and Thionyl Chloride with Vent-Line Traps Catalyzed Synthesis of Silicon Tetrachloride from Higher Tetraalkoxysilanes 33 and Thionyl Chloride Alkoxysilane-Aqueous HCl Investigations Uncatalyzed Synthesis of Trimethylchlorosilane from Trimethylmethoxysilane 36 and Aqueous HCl Uncatalyzed Synthesis of Trimethylchlorosilane from Trimethylethoxysilane 37 and Aqueous HCl Uncatalyzed Synthesis of Triethylchlorosilane from Triethylethoxysilane 38 and Aqueous HCl Alkoxysilane-HCl Gas Investigations Uncatalyzed Synthesis of Methylchlorosilanes from Methylmethoxysilanes 39 and HCl Gas Uncatalyzed and Catalyzed Synthesis of Methylchlorosilanes from 41 Methylethoxysilanes and HCl Gas Uncatalyzed Synthesis of Ethylchlorosilanes from an Ethylmethoxysilanes 43 and HCl Gas Uncatalyzed Synthesis of Ethylchlorosilanes from an Ethylethoxysilanes 44 and HCl Gas Uncatalyzed and Catalyzed Synthesis of Methoxychlorosilanes from 45 Tetramethoxysilanes and HCl Gas iii Uncatalyzed Synthesis of Alkoxychlorosilanes from Higher Tetraalkoxysilanes 49 and HCl Gas Uncatalyzed Synthesis of Alkoxychlorosilanes from Tetramethoxysilane 50 and Liquid HCl Acetoxysilane-Thionyl Chloride Investigations Uncatalyzed Synthesis of Triacetoxychlorosilane and Diacetoxydichlorosilane 51 from Tetraacetoxysilane and Thionyl Chloride Catalyzed Synthesis of Silicon Tetrachloride from Tetraacetoxysilane and 52 Thionyl Chloride Metal Silicate-Chlorinating Agent Investigations Attempted Synthesis of Silicon Tetrachloride from Silicates and 54 Chlorinating Agents Silicon Dioxide-Chlorinating Agent Investigations Attempted Synthesis of Silicon Tetrachloride from Silica and Chlorinating 55 Agents CHAPTER 4. RESULTS AND DISCUSSION OF THE SYNTHESIS OF SiCl4 56 AND CHLOROSILANES Currell’s Approach Experiments Attempts to Reproduce Reported Pyridine HCl-Catalyzed Syntheses of Silicon 57 Tetrachloride from Tetramethoxysilane and Thionyl Chloride Exploratory Experiments Uncatalyzed Synthesis of Silicon Tetrachloride from Tetramethoxysilane and 63 Chlorinating Agents iv Variously Catalyzed Synthesis of Silicon Tetrachloride from Tetramethoxysilane 67 and Chlorinating Agents Detailed Experiments Catalyzed Alkoxysilane-Thionyl Chloride Investigations DMF-Catalyzed Synthesis of Methylchlorosilanes from Methylmethoxysilanes 92 and Thionyl Chloride DMF-Catalyzed Synthesis of Methylchlorosilanes from Methylethoxysilanes 94 and Thionyl Chloride DMF-Catalyzed Synthesis of Ethylchlorosilanes from Ethylalkoxysilanes 95 and Thionyl Chloride DMF-Catalyzed Synthesis of Silicon Tetrachloride from Tetramethoxysilane 96 and Thionyl Chloride Variously Catalyzed Syntheses of Silicon Tetrachloride from Tetramethoxysilane 98 and Thionyl Chloride DMF-Catalyzed Synthesis of Silicon Tetrachloride from Tetramethoxysilane 99 and Thionyl Chloride with Vent-Line Traps Catalyzed Synthesis of Silicon Tetrachloride from Higher Tetraalkoxysilanes 100 and Thionyl Chloride Alkoxysilane-Aqueous HCl Investigations Uncatalyzed Synthesis of Trimethylchlorosilane from Trimethylmethoxysilane 109 and Aqueous HCl v Uncatalyzed Synthesis of Trimethylchlorosilane from Trimethylethoxysilane 111 and Aqueous HCl Uncatalyzed Synthesis of Triethylchlorosilane from Triethylethoxysilane 112 and Aqueous HCl Alkoxysilane-HCl Gas Investigations Silicon Tetrachloride from Tetramethoxysilane and HCl Gas 114 Uncatalyzed Synthesis of Methylchlorosilanes from Methylmethoxysilanes 115 and HCl Gas Uncatalyzed and Catalyzed Synthesis of Methylchlorosilanes from 117 Methylethoxysilanes and HCl Gas Uncatalyzed Synthesis of Ethylchlorosilanes from an Ethylmethoxysilanes 119 and HCl Gas Uncatalyzed Synthesis of Ethylchlorosilanes from an Ethylethoxysilanes 120 and HCl Gas Uncatalyzed and Catalyzed Synthesis of Alkoxychlorosilanes from 122 Tetramethoxysilane and HCl Gas Uncatalyzed Synthesis of Alkoxychlorosilanes from Higher Tetraalkoxysilanes 124 and HCl Gas Acetoxysilane-Thionyl Chloride Investigations Uncatalyzed Synthesis of Triacetoxychlorosilane and Diacetoxydichlorosilane 133 from Tetraacetoxysilane and Thionyl Chloride Catalyzed Synthesis of Silicon Tetrachloride from Tetraacetoxysilane and 136 Thionyl Chloride vi Metal Silicate-Chlorinating Agent Investigations Attempted Synthesis of Silicon Tetrachloride from Silicates and 139 Chlorinating Agents Metal Silicate-Chlorinating Agent Investigations Attempted Synthesis of Silicon Tetrachloride from Silica and Chlorinating 144 Agents CHAPTER 5. SUMMARY AND CONCLUSIONS FOR THE SYNTHESIS OF 147 SiCl4 AND CHLOROSILANES CHAPTER 6. INTRODUCTION TO THE HIGH-ASPECT-RATIO, 160 CONDUCTING AND SEMICONDUCTING NANOWIRES FROM SCROLL POLYMERS Scroll Polymers 161 Objectives 166 CHAPTER 7. PREPARATION AND CHARACTERIZATION OF THE HIGH- 167 ASPECT-RATIO, CONDUCTING AND SEMICONDUCTING NANOWIRES FROM SCROLL POLYMERS Materials and Procedures 168 Instruments and Apparatus 168 Powder X-ray Diffractometry 169 Transmission Electron Microscopy 169 Processing Methods 169 vii CHAPTER 8. EXPERIMENTAL PROCEDURES FOR HIGH-ASPECT-RATIO, 170 CONDUCTING AND SEMICONDUCTING NANOWIRES FROM SCROLL POLYMERS Synthesis of Scroll Polymers Chrysotile Preparation 171 [((CH3)3SiO)x(OH)1-xSiO1.5]n, C-M3 171 C-M3 Fibers Partially Filled with Lead Sulfide 172 C-M3 Fibers Partially Filled with Platinum 173 CHAPTER 9. RESULTS AND DISCUSSION OF THE HIGH-ASPECT-RATIO, 174 CONDUCTING AND SEMICONDUCTING NANOWIRES FROM SCROLL POLYMERS Scroll Nanowires 175 CHAPTER 10. SUMMARY AND CONCLUSIONS OF THE HIGH-ASPECT-RATIO, 180 CONDUCTING AND SEMICONDUCTING NANOWIRES FROM SCROLL POLYMERS APPENDIX A. SELECTED 29Si NMR SPECTRA 182 REFERENCES 208 BIBLIOGRAPHY 213 viii List of Tables Table 1. Boiling Points of Compounds, p 20. Table 2. Reported Pyridine HCl-Catalyzed Synthesis of Silicon Tetrachloride from Tetraalkoxysilanes and Thionyl Chloride – Reaction Conditions and Results, p 60. Table 3. Reported Pyridine HCl-Catalyzed and Nonpyridine Catalyzed Synthesis of Silicon Tetrachloride from Tetraalkoxysilanes and Thionyl Chloride – Reaction Conditions and Results, p 61. Table 4. Reported Pyridine HCl-Catalyzed and Synthesis of Silicon Tetrachloride from Tetraalkoxysilanes and Thionyl Chloride – Reaction Conditions and Results, p 61. Table 5. Attempts to Reproduce Currell’s Reported Pyridine HCl-Catalyzed Syntheses of Silicon Tetrachloride from Tetraalkoxysilanes and Thionyl Chloride, p 62. Table 6. Silanes from a Mixture of Si(OCH3)4 and Various Chlorinating Agents at Various Reaction Times and at Room Temperature - Reaction Mixtures, p 65. Table 7. Silanes from a Mixture of Si(OCH3)4 and Various Chlorinating Agents at Various Reaction Times and at Room Temperature – Results, p 66. Table 8. Silanes from a Mixture of Si(OCH3)4 and Excess of SOCl2 with Thirteen Potential Catalysts and at Various Reaction Times and at Room Temperature - Reaction Mixtures, pp 71 - 72. Table 9. Silanes from a Mixture of Si(OCH3)4 and Excess of SOCl2 with Thirteen Potential Catalysts and at Various