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Wayne State University Wayne State University Dissertations 1-1-2010 Synthesis And Characterization Of Metal Complexes Containing Tetrazolate, Poly(tetrazolyl)borate, And Aryl Pentazole Ligands As High Energy Density Materials Dongmei Lu Wayne State University Follow this and additional works at: http://digitalcommons.wayne.edu/oa_dissertations Part of the Inorganic Chemistry Commons Recommended Citation Lu, Dongmei, "Synthesis And Characterization Of Metal Complexes Containing Tetrazolate, Poly(tetrazolyl)borate, And Aryl Pentazole Ligands As High Energy Density Materials" (2010). Wayne State University Dissertations. Paper 68. This Open Access Dissertation is brought to you for free and open access by DigitalCommons@WayneState. It has been accepted for inclusion in Wayne State University Dissertations by an authorized administrator of DigitalCommons@WayneState. SYNTHESIS AND CHARACTERIZATION OF METAL COMPLEXES CONTAINING TETRAZOLATE, POLY(TETRAZOLYL)BORATE, AND ARYL PENTAZOLE LIGANDS AS HIGH ENERGY DENSITY MATERIALS by DONGMEI LU DISSERTATION Submitted to the Graduate School of Wayne State University, Detroit, Michigan in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY 2010 MAJOR: CHEMISTRY (Inorganic) Approved by: ______________________________ Advisor Date ______________________________ ______________________________ ______________________________ DEDICATION To my parents ii ACKNOWLEDGMENTS I would like to express my sincere gratitude to my advisor, Professor Charles H. Winter, for his guidance and support though the years at Wayne State University. I am grateful to my committee members, Professor Stephanie L. Brock, Professor Jin K. Cha, and Professor Mark Ming-Cheng Cheng, for reviewing my thesis and giving valuable comments and suggestions. I would like to thank Dr. Mary Jane Heeg for determining all the crystal structures, and Dr. Bashar Ksebati for his help with the NMR experiments. I would also like to thank the Winter group former and present members for their useful discussions on my research and friendship. Particularly, I am thankful to Dr. Oussama El-Kadri for helping me learn the glove box and Schlenk line techniques when I first started working in the lab, Dr. Mahesh Karunarathne for sharing his useful crystallization techniques with me, and Dr. Monika K. Wiedmann for translating German literature to English and proof reading my writing while she was around. I would also like to thank my parents, brother, and sister for their continuous love and encouragement. My heartiest thanks go to my husband, Chao Wu, for his love, consideration, and helpful discussions on chemistry during my Ph.D. study. Last but not least, I am also thankful to many others who have given me help and support at Wayne State. All of these help and support have made my studies possible. iii TABLE OF CONTENTS Dedication............................................................................................................. ii Acknowledgements...............................................................................................iii List of Tables ....................................................................................................... vi List of Figures ......................................................................................................vii List of Charts........................................................................................................ ix Chapter 1 – Introduction......................................................................................1 Chapter 2 – Synthesis and Characterization of Heavier Alkaline Earth Metal Tetrazolate Complexes: Potential Energetic Materials and Colorants for Pyrotechnic Compositions........................................28 Chapter 3 – Synthesis and Characterization of Potassium Bis(tetrazolyl)borate Complexes and Their 18-Crown-6 Adducts: Unexpected Boron-Nitrogen Bond Isomerism and Associated Enforcement of κ3-N,N’,H-Ligand Chelation .......................................................40 Chapter 4 – Synthesis and Characterization of Heavier Alkaline Earth Metal Bis(5-methyltetrazolyl)borate Complexes: Transfer of the Bis(tetrazolyl)borate Ligands to Divalent Metal Ions......................76 Chapter 5 – Synthesis and Characterization of Sodium Cyano(tetrazolyl)borate Complexes: Attempted Reactions for the Preparation of Tris(tetrazolyl)borate Ligands with Borohydride Derivatives Other Than KBH4 ..........................100 iv Chapter 6 – Attempted Synthesis of Rhenium(I) Aryl Pentazole Complexes ..........................................................124 Chapter 7 – Conclusion...................................................................................150 Reference .........................................................................................................154 Abstract.............................................................................................................166 Autobiographical Statement..............................................................................168 v LIST OF TABLES Table 1. Crystal data and data collection parameters for 63 and 64............... 49 Table 2. Crystal data and data collection parameters for 66-69...................... 50 Table 3. Selected bond lengths (Å) and angles (°) for 63 ............................... 55 Table 4. Selected bond lengths (Å) and angles (°) for 64 ............................... 57 Table 5. Selected bond lengths (Å) and angles (°) for 66 ............................... 59 Table 6. Selected bond lengths (Å) and angles (°) for 67 ............................... 61 Table 7. Selected bond lengths (Å) and angles (°) for 68 ............................... 63 Table 8. Selected bond lengths (Å) and angles (°) for 69 ............................... 65 Table 9. Crystal data and data collection parameters for 71-73...................... 82 Table 10. Selected bond lengths (Å) and angles (°) for 71 ................................87 Table 11. Selected bond lengths (Å) and angles (°) for 72 ................................89 Table 12. Selected bond lengths (Å) and angles (°) for 73 ................................92 Table 13. Crystal data and data collection parameters for 74-77.....................105 Table 14. Selected bond lengths (Å) and angles (°) for 74 ..............................110 Table 15. Selected bond lengths (Å) and angles (°) for 75 ..............................112 Table 16. Selected bond lengths (Å) and angles (°) for 76 ..............................114 Table 17. Selected bond lengths (Å) and angles (°) for 77 ..............................116 Table 18. Crystal data and data collection parameters for 78, 84, and 89 .......129 Table 19. Selected bond lengths (Å) and angles (°) for 78 ..............................133 Table 20. Selected bond lengths (Å) and angles (°) for 84 ..............................135 Table 21. Selected bond lengths (Å) and angles (°) for 89 ..............................137 vi LIST OF FIGURES Figure 1. TGA traces for 57, 58, and 60 from 20 to 700 oC at 5 oC/min.......... 31 Figure 2. TGA traces for 59, 61, and 62 from 50 to 700 oC at 5 oC/min.......... 32 Figure 3. TGA traces for 39, 63, and 64 from 20 to 500 oC at 5 oC/min...........46 Figure 4. TGA traces for 66-69 from 50 to 700 oC at 5 oC/min ........................47 Figure 5. Perspective view of 63 with thermal ellipsoids at the 50% probability level ............................................................. 54 Figure 6. Perspective view of 64 with thermal ellipsoids at the 50% probability level ............................................................. 56 Figure 7. Perspective view of 66 with thermal ellipsoids at the 50% probability level ............................................................. 58 Figure 8. Perspective view of 67 with thermal ellipsoids at the 50% probability level ............................................................. 60 Figure 9. Perspective view of 68 with thermal ellipsoids at the 50% probability level ............................................................. 62 Figure 10. Perspective view of 69 with thermal ellipsoids at the 50% probability level. ............................................................ 64 Figure 11. TGA traces for 70-73 from 20 to 500 oC at 5 min/oC. ...................... 80 Figure 12. Perspective view of 71 with thermal ellipsoids at the 50% probability level ............................................................. 86 Figure 13. Perspective view of 72 with thermal ellipsoids at the 50% probability level. ............................................................ 88 Figure 14. Perspective view of the inorganic skeleton chain of (SrO2)n in 72... 90 Figure 15. Perspective view of 73 with thermal ellipsoids at the 50% probability level. ............................................................ 91 Figure 16. TGA traces for 74 and 76 from 50 to 500 oC at 5 min/oC. ............. 103 vii Figure 17. Perspective view of 74 with thermal ellipsoids at the 50% probability level. ...........................................................109 Figure 18. Perspective view of 75 with thermal ellipsoids at the 50% probability level ............................................................111 Figure 19. Perspective view of 76 with thermal ellipsoids at the 50% probability level. ...........................................................113 Figure 20. Perspective view of 77 with thermal ellipsoids at the 50% probability level. ...........................................................115
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