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Diaryl Triazenides As Ligands for the Lanthanides and Related Studies

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Diaryl Triazenides As Ligands for the Lanthanides and Related Studies Diaryl Triazenides as Ligands for the Lanthanides and Related Studies A thesis in partial fulfilment of the requirements for the degree of Doctor of Philosophy by Matthew Robert Gyton Supervisor: Assoc. Prof. Marcus L. Cole School of Chemistry Faculty of Science 27th February 2015 Originality Statement 'I hereby declare that this submission is my own work and to the best of my knowledge it contains no materials previously published or written by another person, or substantial proportions of material which have been accepted for the award of any other degree or diploma at UNSW or any other educational institution, except where due acknowledgement is made in the thesis. Any contribution made to the research by others, with whom I have worked at UNSW or elsewhere, is explicitly acknowledged in the thesis. I also declare that the intellectual content of this thesis is the product of my own work, except to the extent that assistance from others in the project's design and conception or in style, presentation and linguistic expression is acknowledged.' Signed ··· ~ ····· · · ··· ········ · ············· Date ... /<-If .. /?!/-£ ..... .. ........... Acknowledgements This thesis would no doubt be far less succesful without the support of many. My heartfelt gratitude is expressed to the following who have helped me to get this far. To my supervisor Marcus Cole, I am grateful for the opportunity to work in this extremely challenging field, a pie, in which I intend to always have a few fingers. I am also thankful for the chance to learn the delicate art of X-ray crystallography, upon which this project was wholly reliant. Secondly I would like to thank my co-supervisor Jason Harper for his invaluable mechanistic insights when my arrow pushing was found wanting, supervision when called upon at times to step-up and help with the initial stages of drafting this thesis. I would like to thank the members of the Cole group both past and present for putting up with my, at times, cantankerous attitude and for keeping me company throughout this PhD. I will always have fond memories of my time with the group, especially the OZOM conference dinners! My thanks must also be extended to the technical staff, who have been so helpful throughout my candidature. First and foremost to Dr Mohan Bhadbhade for his invaluable technical assistance with crystallography and for demonstrating just how truly useful Blu-Tack for repairing goniometer tips! My thanks must also be extended to the staff of the UNSW NMR facility, particularly Drs Don Thomas and Douglas Lawes for their technical and theoretical assistance and all-encompassing knowledge of NMR. I would also like to extend my thanks to my friends who have had my back through thick and thin. In no particular order I would like to thank Steve, Brad, Jo, Sinead, Alasdair, Joana, Hamish, Milena, Rob and the Matts T and P. I will always consider you true friends and I will always look back fondly at UNSW as a result. To my family I am forever thankful for your support. To Holly and Mum particularly: I win. Finally I would like to thank my long suffering girlfriend Sam. I am forever in your debt for your unending support throughout this whole process. I am not sure that I could have done it without you. I am also forever thankful for all the times you didn’t strangle me, even if I did deserve it! Table of Contents Abstract ............................................................................................................................ iv List of Abbreviations......................................................................................................... v Table of Compounds by Number ..................................................................................... xi Chapter I Introduction ................................................................................................ 1 1.1 Introduction to the Lanthanides ....................................................................... 1 1.2 Lanthanide Oxidation States ............................................................................. 3 1.3 Lanthanide Coordination Chemistry ................................................................ 6 1.3.1 Trivalent Lanthanide Cyclopentadienyls .................................................... 7 1.3.2 Divalent Lanthanide Cyclopentadienyls and Heterocyclopentadienyls ... 11 1.3.3 Cerium Cyclopentadienyls, Cyclooctatetraenyls and Pentalenyls ........... 17 1.3.4 Trivalent Lanthanide Amides .................................................................... 18 1.3.5 Divalent Lanthanide Amides ..................................................................... 20 1.3.6 Tetravalent Cerium Amides and Oxidation Chemistry ............................. 23 1.4 Purpose of this Thesis ..................................................................................... 24 Chapter II - Main-Group Metal Complexes of Triazenides and a Formamidinate. 26 2.1 Introduction ..................................................................................................... 26 2.1.1 Main Group Compounds as Synthetic Precursors for Organolanthanide Chemistry ................................................................................................................. 26 2.1.2 Triazenes and Related Amidines ............................................................... 27 2.1.3 Alkali Metal Complexes ............................................................................ 30 2.1.4 Thallium Complexes .................................................................................. 34 2.1.5 Purpose of this Chapter ............................................................................ 35 2.2 Results and Discussion .................................................................................... 36 2.2.1 Synthesis of Triazene Precursors and Triazenes ...................................... 36 2.2.2 Attempts at the Synthesis of a Formamidine from Dipp*NH2................... 49 2.2.3 Synthesis of Alkali Metal Triazenides ....................................................... 67 2.3 Conclusions and Future Work ........................................................................ 81 2.3.1 Conclusions ............................................................................................... 81 2.3.2 Future Work .............................................................................................. 82 i 2.4 Appendix I: Supplementary Crystal Structure ............................................... 84 2.5 Appendix II: Crystal Data for Structures Collected for this Chapter ........... 85 Chapter III Lanthanide Triazenides: Synthesis and Reactivity ............................. 88 3.1 Introduction ..................................................................................................... 88 3.1.1 Trivalent Lanthanide Amidinates and Guanidinates ................................ 88 3.1.2 Divalent Lanthanide Amidinates and Guanidinates ................................. 89 3.1.3 Lanthanide and Actinide Triazenides ....................................................... 91 3.1.4 Purpose of this Chapter ............................................................................ 92 3.2 Results and Discussion .................................................................................... 93 3.2.1 Synthesis of Trivalent Lanthanide Triazenides ......................................... 93 3.2.2 Reactivity of Trivalent Lanthanide Triazenides ...................................... 119 3.2.3 Synthesis of Divalent Lanthanide Triazenides ........................................ 125 3.2.4 Attempts to Synthesise a Tetravalent Cerium Triazenide ....................... 134 3.3 Conclusions and Future Work ...................................................................... 145 3.3.1 Conclusions ............................................................................................. 145 3.3.2 Future Work ............................................................................................ 147 3.4 Appendix III: Supplementary Crystal Structures ........................................ 148 3.5 Appendix IV : Crystal Data for Structures Collected for this Chapter ....... 151 Chapter IV Ytterbium and Calcium Arenes: Unusual Rearrangements Leading to Solvent Separated Ion Pairs ......................................................................................... 155 4.1 Introduction ................................................................................................... 155 4.1.1 The Chemistry of Calcium Arenes .......................................................... 155 4.1.2 The Chemistry of Ytterbium Arenes ........................................................ 158 4.1.3 Solvent Separated Ion Pairs in Calcium and Ytterbium Chemistry ........ 161 4.1.4 Purpose of the Chapter ........................................................................... 163 4.2 Results and Discussion .................................................................................. 163 4.2.1 Synthesis of a Calcium Fluorenide Solvent Separated Ion Pair ............. 163 4.2.2 Synthesis of a Ytterbium Fluorenide Solvent Separated Ion Pair ........... 169 4.4 Appendix V: Crystal Data for Structures Collected for this Chapter .......... 176 Chapter V Experimental .......................................................................................... 177 ii 5.1 General Procedures ....................................................................................... 177
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