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The Synthesis of Kinetically Stabilised Heavy Group 13 Hydride Complexes

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The Synthesis of Kinetically Stabilised Heavy Group 13 Hydride Complexes The Synthesis of Kinetically Stabilised Heavy Group 13 Hydride Complexes Thesis as partial fulfilment of the requirements of Doctor of Philosophy (Chemistry) by Alasdair Iain McKay (Student Number: 3188803) Supervisor: Assoc. Prof. Marcus L. Cole School of Chemistry The University of New South Wales Sydney, Australia 16th April 2015 Certificate of Originality ‘I, Alasdair Iain McKay, 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 projects’ design and conception or in style, presentation and linguistic expression is acknowledged.’ Signed........................................................... Date.............................................................. ii Table of Contents Acknowledgements ix Abstract x Abbreviations xi Chapter One: General Introduction 1 1.1 Group 13 Element Structure 1 1.2 Group 13 Metal Hydrides 3 1.2.1 Bonding and Structure in Group 13 Trihydrides 4 1.2.2 The Thermodynamics of Group 13 Hydrides 5 1.2.3 Lewis Base Adducts of Group 13 Trihydrides 7 1.2.4 Group 13 Halohydride Chemistry 8 1.2.5 Donor Complexes of Group 13 Hydrides 9 1.3 Industrial Applications of Group 13 Hydrides 10 1.3.1 Semiconductor Materials 10 1.3.2 Organic Functional Group Reductions 11 1.4 Low Oxidation State Group 13 Chemistry 12 1.4.1 Synthesis 12 1.4.2 Chemistry 13 1.5 References 14 Chapter Two: Quantification of the Steric and Electronic Character of Monoanionic Bidentate N,Nʹ-Ligands 21 2.1 Introduction 21 2.1.1 Cone Angle 21 2.1.2 Solid Angle 22 2.1.3 Molecular Volumes 25 2.1.4 The Quantification of the Steric Character of High Denticity Ligands 27 2.2 Project Outline 29 2.3 Results and Discussion 30 2.3.1 The Development of a Metal-Based Probe for the Quantification of Monoanionic Bidentate N,N'-Ligands’ Steric Character 30 2.3.1.1 Steric Measurements 31 2.3.1.2 Evaluation of Aluminium as the Basis for a Steric Probe 31 2.3.1.3 Evaluation of Dimethylaluminium as a Steric Probe 34 2.3.1.4 Ligand Intermeshing - A Menacnac Case Study 36 2.3.2 The Preparation of Novel Super-Bulky Bidentate N,N'-Ligands and Evaluation of their Steric Character 40 2.3.2.1 The Synthesis of a 1,3-Bis(2,6-terphenyl)triazene 40 2.3.2.2 The Synthesis of C-2,6-terphenyl Substituted Amidine Ligands 42 2.3.2.3 The Synthesis of Dimethylaluminium Complexes of 1-3 and Popular Ligands 46 iii Table of Contents 2.3.2.4 Steric Measurements of Anionic Bidentate N,N'-Ligands 49 2.3.3 The Development of a Metal-Based Probe to Quantify the Electronic Character of Monoanionic Bidentate N,N'-Ligands 54 2.3.3.1 The Synthesis of Rhodium Bis(carbonyl) Complexes 57 2.3.3.2 Electronic Measurements for the Monoanionic Bidentate N,N'-Ligands Studied Herein 60 2.3.3.3 Structural Studies of Rhodium Complexes 11-18 63 2.3.4 The Development of a Second Generation Steric Probe 69 2.4 Conclusions 73 2.5 Future Directions 75 2.6 Experimental 76 2.6.1 General Synthetic Procedures 76 2.6.2 Synthesis of Dmp2N3H (1) 76 2.6.3 Synthesis of DitopACyH (2) 76 2.6.4 Synthesis of DmpACyH (3) 77 2.6.5 General Procedure for the Preparation of Dimethylaluminium Complexes 78 Me 2.6.6 Synthesis of [AlMe2( Aiso)] (10) 80 2.6.7 General Procedure for the Preparation of Rhodium Carbonyl Complexes 81 2.6.8 Synthesis of [Rh(Fiso)(cod)] (17) 82 2.6.9 Synthesis of [Rh(N3Dipp2)(cod)] (18) 83 2.6.10 General Procedure for the Carbonylation of Rhodium 1,5-cod Complexes 84 2.7 References 85 Chapter Three: Alkali Metal Complexes of Bulky Bidentate N,N'-Ligands 96 3.1 Introduction 96 3.1.1 β-Diketiminate Complexes 96 3.1.2 Amidinate, Guanidinate and Triazenide Complexes 97 3.2 Project Outline 101 3.3 Results and Discussion 102 3.3.1 The Synthesis of Ether Solvated Lithium Amidinate Complexes 102 3.3.2 The Synthesis of Ether Solvated Lithium Triazenide Complexes 106 3.3.3 Donor-Free Monomeric Alkali Metal Triazenide Complexes and a Less Hindered Aggregate 109 3.3.4 Bimetallic Triazenide Complexes 120 3.4 Conclusions 123 3.5 Future Directions 125 3.6 Experimental 126 3.6.1 General Synthetic Procedures 126 3.6.2 General Synthetic Procedure for the Preparation of Lithium Amidinate Complexes 126 3.6.3 General Synthetic Procedure for the Preparation of Ether Solvated Lithium Triazenide Complexes 127 iv Table of Contents 3.6.4 Synthesis of [{Li(N3Dipp2)}x] (28) 128 3.6.5 Synthesis of [{K(N3Dipp2)}x] (29) 129 3.6.6 Synthesis of [Li(N3Dmp2)] (30) 129 3.6.7 Synthesis of [Na(N3Dmp2)] (31) 130 3.6.8 Synthesis of [K(N3Dmp2)] (32) 130 3.6.9 Synthesis of [Rb(N3Dmp2)] (33) 131 3.6.10 Synthesis of [Cs(N3Dmp2)] (34) 131 1 n 3.6.11 Synthesis of [Li2(μ-κ -N3Dmp2)(μ- Bu)] (36) 132 3.7 References 133 Chapter Four: Stabilisation of Low Oxidation State Group 13 Complexes by Kinetic Control 138 4.1 Introduction 138 4.1.1 Halides 138 4.1.2 Alkyl, Amide, Cyclopentadienyl and Silyl Clusters 139 4.1.3 Bulky Aryl and Amide Complexes 141 4.1.4 Anionic Polydentate N-Donor Ligands 142 4.1.5 The Oxidative Chemistry of MIL Species 144 4.1.6 The Coordination Chemistry of MIL Species 145 4.2 Project Outline 148 4.3 Results and Discussion 149 4.3.1 Attempted Stabilisation of Low Oxidation State Group 13 Metals using a 1,3-Bis(aryl)triazenide 149 4.3.2 Kinetic Stabilisation of Low Oxidation State Group 13 Metals using a 1,3-Bis(2,6-terphenyl)triazenide 156 4.3.3 The Chemistry of Group 13 Metal(I) Triazenide Complexes 160 4.4 Conclusions 162 4.5 Future Directions 163 4.6 Experimental 165 4.6.1 General Synthetic Procedures 165 4.6.2 Synthesis of [GaI(N3Dipp2)2] (37) 165 4.6.3 Synthesis of [{GaI(N3Dipp2)}2] (38) 165 4.6.4 Synthesis of [GaCl(N3Dipp2)2] (39) 166 4.6.5 Synthesis of [InCl(N3Dipp2)2] (40) 166 4.6.6 Synthesis of [InI(N3Dipp2)2] (41) 167 4.6.7 The Reaction of InCp with Dipp2N3H 168 4.6.8 Synthesis of [{Tl(N3Dipp2)}2] (42) 168 4.6.9 Synthesis of [Ga(N3Dmp2)] (43) 168 4.6.10 Synthesis of [In(N3Dmp2)] (44) 169 4.6.11 Synthesis of [Tl(N3Dmp2)] (45) 169 4.6.12 Attempted Preparation of B(C6F5)3 Adducts of 42-45 170 4.6.13 The Reaction of [Ni(cdt)] with 44 170 v Table of Contents 4.6.14 The Reaction of [Pd2(dvds)3] with 44 170 4.7 References 171 Chapter Five: Triazenide Complexes of Trivalent Group 13 Metal Halides and Alkyls 180 5.1 Introduction 180 5.1.1 β-Diketiminate Complexes 180 5.1.2 Amidinate Complexes 181 5.1.3 1,3-Triazenide Complexes 183 5.1.4 Reactivity 184 5.2 Project Outline 185 5.3 Results and Discussion 186 5.3.1 Triazenide Complexes of the Dihalo Group 13 Metals 186 5.3.2 Triazenide Complexes of the Dimethyl Group 13 Metals 192 5.4 Conclusions 197 5.5 Future Directions 198 5.6 Experimental 199 5.6.1 General Synthetic Procedures 199 5.6.2 Synthesis of [AlCl2(N3Dmp2)] (46) 199 5.6.3 Synthesis of [GaCl2(N3Dmp2)] (47) 199 5.6.4 Synthesis of [InBr2(N3Dmp2)] (48) 200 5.6.5 Synthesis of [SiMe3(N3Dmp2)] (49) 200 5.6.6 Attempted Synthesis of [TlX2(N3Dmp2)] (X = halide) 201 5.6.7 Synthesis of [GaMe2(N3Dmp2)] (50) 202 5.6.8 Synthesis of [InMe2(N3Dmp2)] (51) 202 5.6.9 Synthesis of [TlMe2(N3Dmp2)] (52) 203 5.7 References 204 Chapter Six: Stabilisation of Group 13 Hydrides with Triazenide Ligands 208 6.1 Introduction 208 6.1.1 β-Diketiminate Complexes 208 6.1.2 Amidinate and Guanidinate Complexes 210 6.1.3 Triazenide Complexes 213 6.1.4 The Reactivity of Group 13 Hydride Complexes 215 6.2 Project Outline 216 6.3 Results and Discussion 217 6.3.1 The Stabilisation of M-H Bonds with C-2,6-Terphenyl Substituted Amidinate Ligands 217 6.3.2 The Stabilisation of M-H Bonds by N-Aryl Triazenide Ligands 221 6.3.3 The Stabilisation of M-H Bonds with an N-2,6-Terphenyl Triazenide Ligand 231 6.4 Conclusions 238 vi Table of Contents 6.5 Future Directions 240 6.6 Experimental 241 6.6.1 General Synthetic Procedures 241 6.6.2 Preparation of [LiInH4] 241 Ditop 6.6.3 Synthesis of [AlH( ACy)2] (53) 241 6.6.4 Synthesis of [AlH(N3Dipp2)2] (54) 242 6.6.5 Synthesis of [GaH(N3Dipp2)2] (55) 242 6.6.6 Synthesis of [InH(N3Dipp2)2] (56) 243 6.6.7 Synthesis of [TlCl(N3Dipp2)2] (57) 243 6.6.8 Synthesis of [TlBr(N3Dipp2)2] (58) 244 6.6.9 The Attempted Synthesis of [TlH(N3Dipp2)2] 244 6.6.10 Synthesis of [AlH2(N3Dmp2)] (59) 245 6.6.11 Synthesis of [GaH2(N3Dmp2)] (60) 245 6.6.12 Attempted Synthesis of [InH2(N3Dmp2)] 246 6.7 References 247 Chapter Seven: Stabilisation of Heavy Group 13 Trihydrides with N-Heterocyclic Carbenes 251 7.1 Introduction 251 7.1.1 Amine and Phosphine Complexes of Group 13 Metallanes 251 7.1.2 NHC Complexes of Group 13 Metallanes 254 7.1.3 The Stabilisation of 6th Period Metal Hydride Moieties with NHCs 256 7.1.4 Super Bulky NHCs 258 7.2 Project Outline 259 7.3 Results and Discussion 260 7.3.1 The Role of Sterics in the Stability of NHC Complexes of Alane 260 7.3.2 The Stability of NHC Complexes of Indane 262 7.3.3 Preliminary Studies of the Reactivity of the Indane and Gallane Complexes Developed Herein with Group 6 Carbonyls 284 7.4 Conclusions 293 7.5 Future Directions 295 7.6 Experimental 296 7.6.1 General Synthetic Procedures 296 7.6.2 Synthesis of [AlH3(IMe)] (61) 296 7.6.3 Synthesis of [InH3(7Dipp)] (62) 296 7.6.4 Intentional Synthesis of 7Dipp·HH
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