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Gordenj019.Pdf Copyright by John David Gorden 2001 The Dissertation Committee for John David Gorden Certifies that this is the approved version of the following dissertation: Low Valent and Mixed Valent Cyclopentadienyl Complexes of the Group 13 Elements Committee: Alan H. Cowley, Supervisor Richard A. Jones Richard J. Lagow John G. Ekerdt Jason B. Shear Low Valent and Mixed Valent Cyclopentadienyl Complexes of the Group 13 Elements by John David Gorden, B.S. Dissertation Presented to the Faculty of the Graduate School of The University of Texas at Austin in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy The University of Texas at Austin December, 2001 For Anne Your love will always be my greatest discovery. Acknowledgements First of all I would like to thank my supervising professor, Dr. Alan H. Cowley. I am extremely grateful for all of his intellectual guidance, support, and for the risk he took with this academically suspect student. I wish to express my appreciation to Dr. Charles Macdonald for helping me find focus in my work. His infectious enthusiasm for all areas chemistry has encouraged us all. I would also like to thank Dr. Richard Jones for his help throughout my time here. Special thanks go out to my generation of the Cowley research group for their help, friendship, and tolerance. A collective thanks to Dr. Andreas Voigt, Rob Wiacek, Jeff Pietryga, Piyush Shukla, Jamie Jones, Dr. Jason Clyburne, Dr. Colin Abernethy, Dr. Brian McBurnett, Dr. Vivianna Lomelli, Joel Silverman. I would like to also thank Dr. Vincent Lynch for his help with some of the X-ray work presented here. My heartfelt gratitude to Julie Campos for keeping everything running smoothly and for always providing a willing ear I needed to vent. I would like to express deep appreciation for the love and support of my parents, family, and in-laws, without which none of this would have been possible. I wish to thank the Dorothy Banks Charitable Trust for their financial support in the form of a Graduate Research Fellowship as well as the National Science Foundation, the Robert A. Welch Foundation and the National Academy of Sciences through Sigma Xi. Finally, and most of all, I would like to thank my wife Anne for her never- ending love, support and understanding. She has endured too much time alone, and too many long distance conversations during the course of these studies. v Low Valent and Mixed Valent Cyclopentadienyl Complexes of the Group 13 elements Publication No._____________ John David Gorden, Ph.D. The University of Texas at Austin, 2001 Supervisor: Alan H. Cowley A variety of low-coordinate bonding environments that feature group 13 elements have been explored. The highlights in this area include the isolation and structural characterization of the decamethylborocenium cation, the most tightly squeezed metallocene and the first compound to adopt a s/p geometry in the solid state, the synthesis of the first gallocenium cation, the first examples of main group constrained geometry compounds, and the first examples of multidecker p-block cations. The reactivities of monovalent group 13 pentamethylcyclopentadienide compounds with conjugated systems and electron-deficient tris(perfluorophenyl) compounds has also been explored. It has been found that [(C5Me5)M]n (M = Al, Ga) fragments will undergo oxidative addition to diazabutadienes, resulting in the formation of monomeric five-membered ring systems. Furthermore, it has been vi shown that the reactions of [(C5Me5)M]n clusters (M = Al, Ga) with (C6F5)3M (M = B, Al, Ga, In) yield the first examples of group 13 M(I)-M(III) donor-acceptor complexes, the first valence isomer of a dialane, and a unique inverse sandwich complex featuring p-bonding to perfluorophenyl ligands. It has further been found that the reactions of (C5Me5)2AlMe and (C5Me5)3Ga with tetramethylimidazol-2-ylidene yield unprecedented (C5Me5)2MH carbene complexes and tetramethylfulvene. vii Table of Contents List of Tables......................................................................................................x List of Figures .................................................................................................xiv Chapter 1. General Introduction.....................................................................1 Introduction.................................................................................................1 References and Notes ................................................................................12 Chapter 2. Synthesis and Structure of Group 13 Cations ............................15 Introduction...............................................................................................15 Section 2.1 Metallocenium Cation Precursors............................................22 Section 2.2 Borocenium Cations................................................................36 Section 2.3 Aluminocenium Cations..........................................................42 Section 2.4 Gallocenium Cations...............................................................51 Section 2.5 Constrained Geometry Complexes ..........................................66 Section 2.6 Multidecker Cations................................................................75 Experimental.............................................................................................83 Tables of Crystallographic and Theoretical Data .....................................100 References and Notes ..............................................................................151 Chapter 3. Reactions with Monovalent Group 13 Cyclopentadienides......159 Introduction.............................................................................................159 Section 3.1 Cycloadditions ......................................................................167 Section 3.2 Al(I) Donor-Acceptor Complexes .........................................178 Section 3.3 Ga(I) Donor-Acceptor Complexes.........................................189 Section 3.4 In(I) Complexes ....................................................................197 Experimental...........................................................................................203 Tables of Crystallographic and Theoretical Data .....................................213 References and Notes ..............................................................................232 viii Chapter 4. Reactions of Group 13 Cyclopentadienides with a Nucleophilic Carbene.................................................................241 Introduction.............................................................................................241 Results and Discussion............................................................................167 Experimental...........................................................................................249 Tables of Crystallographic Data ..............................................................254 References and Notes ..............................................................................261 Appendix. Listing of Compound Numbers by Chapters............................263 Vita ................................................................................................................265 ix List of Tables Table 1.1. Selected Properties of the Group 13 Elements………………………3 Table 1.2. Electronegativities and Radii of Non-Group 13 Elements…………..3 Table 1.3 Selected Thermodynamic Properties of Group 13 Elements………..4 1 Table 2.1. Crystal Data and Structure Refinement for (h -C5Me5)2BBr……. 102 1 Table 2.2. Selected Bond Lengths [Å] for (h -C5Me5)2BBr………………… 103 1 Table 2.3. Selected Bond Angles [°] for (h -C5Me5)2BBr………………….. 103 1 Table 2.4. Crystal Data and Structure Refinement for (h -C5Me5)2BMe…… 105 1 Table 2.5. Selected Bond Lengths [Å] for (h -C5Me5)2BMe……………….. 106 1 Table 2.6. Selected Bond Angles [°] for (h -C5Me5)2BMe…………………. 106 1 Table 2.7. Crystal Data and Structure Refinement for (h -C5Me5)2GaCl….. 108 1 Table 2.8. Selected Bond Lengths for (h -C5Me5)2GaCl…………………… 109 1 Table 2.9. Selected Bond Angles [°] for (h -C5Me5)2GaCl………………… 109 Table 2.10. Crystal Data and Structure Refinement for 1 2 (h -C5Me5)(h -5Me5)2GaMe…………………………………….. 111 1 2 Table 2.11. Selected Bond Lengths for (h -C5Me5)(h -C5Me5)GaMe……….. 112 1 2 Table 2.12. Selected Bond Angles [°] for (h -C5Me5)(h -C5Me5)GaMe…….. 112 Table 2.13. Crystal Data and Structure Refinement for 1 5 + - [(h -C5Me5)(h -C5Me5)B] [AlCl4] ……………………...………. 114 Table 2.14. Selected Bond Lengths [Å] for 1 5 + - [(h -C5Me5)(h -C5Me5)B] [AlCl4] …………….……………….. 115 Table 2.15. Selected Bond Angles [°] for 1 5 + - [(h -C5Me5)(h -C5Me5)B] [AlCl4] ……………………………… 115 + Table 2.16. Selected BP86 Calculation Results for [(h-C5H5)2B] Cations….. 116 Table 2.17. Crystal Data and Structure Refinement for 5 [(h -C5Me5)(C6F5)AlCl]2………………………………………… 118 5 Table 2.18. Selected Bond Lengths [Å] for [(h -C5Me5)(C6F5)AlCl]2………. 119 5 Table 2.19. Selected Bond Angles [°] for [(h -C5Me5)(C6F5)AlCl]2………… 119 x Table 2.20. Crystal Data and Structure Refinement for 5 + - [(h -C5Me5)2Al] [AlCl4] ………………………………………… 121 Table 2.21. Selected Bond Lengths [Å] for 5 + - [(h -C5Me5)2Al] [AlCl4] ………………………………………… 122 5 + - Table 2.22. Selected Bond Angles [°] for [(h -C5Me5)2Al] [AlCl4] ………… 122 Table 2.23. Crystal Data and Structure Refinement for 3 [(h -C5Me5)(C6F5)GaCl]2………………………………………... 124 3 Table 2.24. Selected Bond Lengths [Å] for [(h -C5Me5)(C6F5)GaCl]2………. 125 3 Table 2.25. Selected Bond Angles
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