Lanthanide and Actinide Chemistry

About the Author xiii Preface to the Second Edition xiv Preface to the First Edition xv About the Companion Website xvi 1 Introduction to the Lanthanides 1 1.1 Introduction 1 1.2 Characteristics of the Lanthanides 2 1.3 Occurrence and Abundance of the Lanthanides 2 1.4 Lanthanide Ores 3 1.5 Extracting and Separating the Lanthanides 5 1.5.1 Extraction 5 1.5.2 Separating the Lanthanides 5 1.6 The Position of the Lanthanides in the Periodic Table 8 1.7 The Lanthanide Contraction 8 1.8 Recycling Lanthanides 8 1.9 Isotopes 9 2 The Lanthanides – Principles and Energetics 13 2.1 Electron Configurations of the Lanthanides and f Orbitals 13 2.2 What Do f Orbitals Look Like? 14 2.3 How f Orbitals Affect Properties of the Lanthanides 15 2.4 The Lanthanide Contraction 16 2.5 Electron Configurations of the Lanthanide Elements and of Common Ions 16 2.6 Patterns in Ionization Energies 17 2.7 Atomic and Ionic Radii 18 2.8 Patterns in Hydration Energies (Enthalpies) for the Lanthanide Ions 19 2.9 Enthalpy Changes for the Formation of Simple Lanthanide Compounds 20 2.9.1 Stability of Tetrahalides 20 2.9.2 Stability of Dihalides 22 2.9.3 Stability of Aqua Ions 23 2.10 Patterns in Redox Potentials 24 3 The Lanthanide Elements and Simple Binary Compounds 28 3.1 Introduction 28 3.2 The Elements 28 3.2.1 Properties 28 3.2.2 Synthesis 29 3.2.3 Alloys and Uses of the Metals 30 3.3 Binary Compounds 30 3.3.1 Trihalides 30 3.3.2 Tetrahalides 32 3.3.3 Dihalides 32 3.3.4 Oxides 34 3.4 Borides 36 3.5 Carbides 36 3.6 Nitrides 37 3.7 Hydrides 37 3.8 Sulfides 37 4 Coordination Chemistry of the Lanthanides 40 4.1 Introduction 40 4.2 Stability of Complexes 40 4.3 Complexes 42 4.3.1 The Aqua Ions 42 4.3.2 Hydrated Salts 43 4.3.3 Other O-Donors 44 4.3.4 Complexes of β-Diketonates 46 4.3.5 Lewis Base Adducts of β-Diketonate Complexes 47 4.3.6 Nitrate and Carbonate Complexes 47 4.3.7 Crown Ether Complexes 48 4.3.8 Complexes of EDTA and Related Ligands 49 4.3.9 Complexes of N-Donors 50 4.3.10 Complexes of Porphyrins and Related Systems 51 4.3.11 Halide Complexes 52 4.3.12 Complexes of S-Donors 52 4.4 Alkoxides, Alkylamides, and Related Substances 53 4.4.1 Alkylamides 53 4.4.2 Alkoxides 54 4.4.3 Thiolates 56 4.4.4 Borohydrides 57 4.5 Coordination Numbers in Lanthanide Complexes 57 4.5.1 General Principles 57 4.5.2 Examples of the Coordination Numbers 58 4.5.3 The Lanthanide Contraction and Coordination Numbers 60 4.5.4 Formulae and Coordination Numbers 63 4.6 The Coordination Chemistry of the +2 and +4 States 63 4.6.1 The (+2) State 63 4.6.2 The (+4) State 66 4.7 Lanthanides in Living Systems 69 5 Electronic and Magnetic Properties of the Lanthanides 76 5.1 Magnetic and Spectroscopic Properties of the Ln3+ Ions 76 5.2 Magnetic Properties of the Ln3+ Ions 77 5.2.1 Adiabatic Demagnetization 79 5.2.2 Single Molecule Magnets (SMMs) and Single Ion Magnets (SIMs) 80 5.3 Energy-Level Diagrams for the Lanthanide Ions, and Their Electronic Spectra 84 5.3.1 Electronic Spectra 84 5.3.2 Hypersensitive Transitions 86 5.4 Luminescence Spectra 87 5.4.1 Quenching 92 5.4.2 Antenna Effects 92 5.4.3 Lanthanides in Upconversion 93 5.4.4 Applications of Luminescence to Sensory Probes 95 5.4.4.1 Terbium Luminescence to Detect Anthrax 97 5.4.4.2 Fingerprint Detection 97 5.4.5 Fluorescence and TV 98 5.4.6 Lighting Applications 99 5.4.7 Lasers 99 5.4.8 Euro Banknotes 100 5.5 NMR Applications 100 5.5.1 β-Diketonates as NMR Shift Reagents 100 5.5.2 Magnetic Resonance Imaging (MRI) 102 5.5.3 What Makes a Good MRI Agent? 102 5.5.4 Health Issues with MRI Agents 104 5.5.5 Texaphyrins 104 5.6 Electron Paramagnetic Resonance Spectroscopy 105 5.7 Lanthanides as Probes in Biological Systems 105 6 Organometallic Chemistry of the Lanthanides 110 6.1 Introduction 110 6.2 The +3 Oxidation State 110 6.2.1 Alkyls 111 6.2.2 Aryls 112 6.3 Cyclopentadienyls 113 6.3.1 Compounds of the Unsubstituted Cyclopentadienyl Ligand (C5H5 = Cp; C5Me5 =Cp∗) 113 6.3.2 Compounds [LnCp∗3] (Cp∗ = Pentamethylcyclopentadienyl) 116 6.3.3 Bis(cyclopentadienyl) Alkyls and Aryls LnCp2R 117 6.3.4 Bis(pentamethylcyclopentadienyl) Alkyls 118 6.3.5 Hydride Complexes 121 6.4 Cyclooctatetraene Dianion Complexes 121 6.5 The +2 State 122 6.5.1 Alkyls and Aryls 122 6.5.2 Cyclopentadienyls 123 6.5.3 Other Compounds 126 6.6 The +4 State 126 6.7 Metal–Arene Complexes 128 6.8 Carbonyls 129 6.9 Compounds with Lanthanide-Metal Bonds 129 7 The Misfits: Scandium, Yttrium, and Promethium 134 7.1 Introduction 134 7.2 Scandium 134 7.2.1 Binary Compounds of Scandium 135 7.3 Coordination Compounds of Scandium 136 7.3.1 The Aqua Ion and Hydrated Salts 136 7.3.2 Other Complexes 137 7.3.3 Alkoxides and Alkylamides 139 7.3.4 Patterns in Coordination Number 140 7.3.5 Scandium and Yttrium in the (+2) State 144 7.4 Organometallic Compounds of Scandium 145 7.5 Yttrium 148 7.6 Promethium 149 8 Introduction to the Actinides 154 8.1 Introduction and Occurrence of the Actinides 154 8.2 Synthesis 155 8.3 Extraction of Th, Pa, and U 157 8.3.1 Extraction of Thorium 157 8.3.2 Extraction of Protactinium 157 8.3.3 Extraction and Purification of Uranium 157 8.3.4 Uranium Extraction from Seawater 157 8.4 Uranium Isotope Separation 159 8.4.1 Gaseous Diffusion 159 8.4.2 Gas Centrifuge 160 8.4.3 Electromagnetic Separation 160 8.4.4 Laser Separation 160 8.5 Characteristics of the Actinides 160 8.6 Reduction Potentials of the Actinides 162 8.7 Relativistic Effects 163 9 Binary Compounds of the Actinides 165 9.1 Introduction 165 9.2 Halides 165 9.2.1 Syntheses of the Halides 167 9.2.2 Structure Types 168 9.3 Thorium Halides 170 9.4 Uranium Halides 170 9.4.1 Uranium(VI) Compounds 170 9.4.2 Uranium(V) Compounds 172 9.4.3 Uranium(IV) Compounds 172 9.4.4 Uranium(III) Compounds 173 9.4.5 Uranium Hexafluoride and Isotope Separation 173 9.5 Actinide Halides (Ac–Am) Excluding U and Th 175 9.5.1 Actinium 175 9.5.2 Protactinium 175 9.5.3 Neptunium 176 9.5.4 Plutonium 177 9.5.5 Americium 177 9.6 Halides of the Heavier Transactinides 178 9.6.1 Curium(III) Chloride 178 9.6.2 Californium(III) Chloride, Californium(III) Iodide, and Californium(II) Iodide 178 9.6.3 Einsteinium(II) Chloride 179 9.7 Oxides 179 9.7.1 Thorium Oxide 179 9.7.2 Uranium Oxides 180 9.7.3 Plutonium Oxides 180 9.8 Sulfides 180 9.9 Uranium Hydride UH3 181 9.10 Oxyhalides 181 10 Coordination Chemistry of the Actinides 184 10.1 Introduction 184 10.2 General Patterns in the Coordination Chemistry of the Actinides 185 10.3 Coordination Numbers in Actinide Complexes 185 10.4 Types of Complex Formed 187 10.5 Uranium and Thorium Chemistry 187 10.5.1 Uranyl Complexes 187 10.5.2 Coordination Numbers and Geometries in Uranyl Complexes 190 10.5.3 Some Other Complexes 192 10.5.4 Uranyl Nitrate and Its Complexes; Their Role in Processing Nuclear Waste 193 10.5.5 Nuclear Waste Processing 193 10.5.6 Uranium Oxo Complexes 194 10.5.7 Uranium Nitrido Complexes 195 10.5.8 Uranium(V) Complexes 196 10.5.9 Uranium(III) Complexes 197 10.5.10 Uranium(II) Complexes 198 10.6 Complexes of the Actinide(IV) Nitrates and Halides 199 10.6.1 Thorium Nitrate Complexes 199 10.6.2 Uranium(IV) Nitrate Complexes 200 10.6.3 Complexes of the Actinide(IV) Halides 200 10.7 Thiocyanates 202 10.8 Amides, Alkoxides, and Thiolates 203 10.8.1 Amide Chemistry 203 10.8.2 Alkoxides and Aryloxides 207 10.8.3 Borohydrides 209 10.8.4 Uranium Chelate Compounds 209 10.9 Chemistry of Actinium 210 10.10 Chemistry of Protactinium 211 10.11 Chemistry of Neptunium 212 10.11.1 Complexes of Neptunium 213 10.12 Chemistry of Plutonium 214 10.12.1 Aqueous Chemistry 214 10.12.2 Stability of the Oxidation States of Plutonium 215 10.12.3 Coordination Chemistry of Plutonium 216 10.12.4 Plutonium in the Environment 218 10.13 Chemistry of Americium and Subsequent Actinides 220 10.13.1 Potentials 220 10.14 Chemistry of the Later Actinides 222 11 Electronic and Magnetic Properties of the Actinides 228 11.1 Introduction 228 11.2 Absorption Spectra 229 11.2.1 Uranium (VI) – UO22+ – f0 229 11.2.2 Uranium(V) – f1 230 11.2.3 Uranium(IV) – f2 230 11.2.4 Spectra of the Later Actinides 233 11.3 Magnetic Properties 234 11.3.1 Uranium Single Molecule Magnets 236 12 Organometallic Chemistry of the Actinides 238 12.1 Introduction 238 12.2 Simple σ-Bonded Organometallics 238 12.3 Cyclopentadienyls 242 12.3.1 Oxidation State (VI) 242 12.3.2 Oxidation State (V) 242 12.3.3 Oxidation State (IV) 242 12.3.4 Oxidation State (III) 245 12.4 Compounds of the Pentamethylcyclopentadienyl Ligand (C5Me5 =Cp∗) 246 12.4.1 Oxidation State (IV) 246 12.4.2 Cationic Species and Catalysts 247 12.4.3 Hydrides 248 12.4.4 Oxidation State (III) 249 12.4.5 Oxidation State (II) 249 12.4.6 Some Recent Chemistry of Neptunium and Plutonium 251 12.5 Tris(pentamethylcyclopentadienyl) Systems 252 12.6 Other Metallacycles 252 12.7 Cyclooctatetraene Dianion Compounds 253 12.8 Arene Complexes 254 12.8.1 Simple Arene Derivatives 254 12.8.2 Arene-Supported Triazacyclononane Derivatives 254 12.9 Carbonyls 256 12.10 Compounds with Actinide-metal Bonds 257 13 Synthesis of the Transactinides and Their Chemistry 260 13.1 Introduction 260 13.2 Finding New Elements 261 13.3 Synthesis of the Transactinides 261 13.4 Naming the Transactinides 265 13.5 Predicting Electronic Arrangements 266 13.6 Identifying the Elements 266 13.7 Predicting Chemistry of the Transactinides 272 13.8 What Is Known about the Chemistry of the Transactinides 273 13.8.1 Element 104 273 13.8.2 Element 105 273 13.8.3 Element 106 274 13.8.4 Element 107 274 13.8.5 Element 108 274 13.8.6 Elements 112 and 114 276 13.9 And the Future? 276 References 278 Index 310