Lanthanide and Actinide Chemistry - Simon Cotton

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Résumé :

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 ?-Diketonates 46

4.3.5 Lewis Base Adducts of ?-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 ...

Biographie:
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 ?-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