SIMON COTTON, PHD, is a retired Honorary Senior Lecturer in Chemistry at the University of Birmingham, UK. He has decades of teaching and publishing experience in inorganic chemistry and related fields, and first worked with uranium and the lanthanides over fifty years ago; his ‘Soundbite Molecules’ column regularly appeared In the magazine Education in Chemistry for fifteen years, whilst he has written over 100 ‘Molecules of the Month’ at https://www.chm.bris.ac.uk/motm/motm.htm

• About the Author xiiiPreface to the Second Edition xivPreface to the First Edition xvAbout the Companion Website xvi1 Introduction to the Lanthanides 11.1 Introduction 11.2 Characteristics of the Lanthanides 21.3 Occurrence and Abundance of the Lanthanides 21.4 Lanthanide Ores 31.5 Extracting and Separating the Lanthanides 51.5.1 Extraction 51.5.2 Separating the Lanthanides 51.6 The Position of the Lanthanides in the Periodic Table 81.7 The Lanthanide Contraction 81.8 Recycling Lanthanides 81.9 Isotopes 92 The Lanthanides – Principles and Energetics 132.1 Electron Configurations of the Lanthanides and f Orbitals 132.2 What Do f Orbitals Look Like? 142.3 How f Orbitals Affect Properties of the Lanthanides 152.4 The Lanthanide Contraction 162.5 Electron Configurations of the Lanthanide Elements and of Common Ions 162.6 Patterns in Ionization Energies 172.7 Atomic and Ionic Radii 182.8 Patterns in Hydration Energies (Enthalpies) for the Lanthanide Ions 192.9 Enthalpy Changes for the Formation of Simple Lanthanide Compounds 202.9.1 Stability of Tetrahalides 202.9.2 Stability of Dihalides 222.9.3 Stability of Aqua Ions 232.10 Patterns in Redox Potentials 243 The Lanthanide Elements and Simple Binary Compounds 283.1 Introduction 283.2 The Elements 283.2.1 Properties 283.2.2 Synthesis 293.2.3 Alloys and Uses of the Metals 303.3 Binary Compounds 303.3.1 Trihalides 303.3.2 Tetrahalides 323.3.3 Dihalides 323.3.4 Oxides 343.4 Borides 363.5 Carbides 363.6 Nitrides 373.7 Hydrides 373.8 Sulfides 374 Coordination Chemistry of the Lanthanides 404.1 Introduction 404.2 Stability of Complexes 404.3 Complexes 424.3.1 The Aqua Ions 424.3.2 Hydrated Salts 434.3.3 Other O-Donors 444.3.4 Complexes of β-Diketonates 464.3.5 Lewis Base Adducts of β-Diketonate Complexes 474.3.6 Nitrate and Carbonate Complexes 474.3.7 Crown Ether Complexes 484.3.8 Complexes of EDTA and Related Ligands 494.3.9 Complexes of N-Donors 504.3.10 Complexes of Porphyrins and Related Systems 514.3.11 Halide Complexes 524.3.12 Complexes of S-Donors 524.4 Alkoxides, Alkylamides, and Related Substances 534.4.1 Alkylamides 534.4.2 Alkoxides 544.4.3 Thiolates 564.4.4 Borohydrides 574.5 Coordination Numbers in Lanthanide Complexes 574.5.1 General Principles 574.5.2 Examples of the Coordination Numbers 584.5.3 The Lanthanide Contraction and Coordination Numbers 604.5.4 Formulae and Coordination Numbers 634.6 The Coordination Chemistry of the +2 and +4 States 634.6.1 The (+2) State 634.6.2 The (+4) State 664.7 Lanthanides in Living Systems 695 Electronic and Magnetic Properties of the Lanthanides 765.1 Magnetic and Spectroscopic Properties of the Ln3+ Ions 765.2 Magnetic Properties of the Ln3+ Ions 775.2.1 Adiabatic Demagnetization 795.2.2 Single Molecule Magnets (SMMs) and Single Ion Magnets (SIMs) 805.3 Energy-Level Diagrams for the Lanthanide Ions, and Their Electronic Spectra 845.3.1 Electronic Spectra 845.3.2 Hypersensitive Transitions 865.4 Luminescence Spectra 875.4.1 Quenching 925.4.2 Antenna Effects 925.4.3 Lanthanides in Upconversion 935.4.4 Applications of Luminescence to Sensory Probes 955.4.4.1 Terbium Luminescence to Detect Anthrax 975.4.4.2 Fingerprint Detection 975.4.5 Fluorescence and TV 985.4.6 Lighting Applications 995.4.7 Lasers 995.4.8 Euro Banknotes 1005.5 NMR Applications 1005.5.1 β-Diketonates as NMR Shift Reagents 1005.5.2 Magnetic Resonance Imaging (MRI) 1025.5.3 What Makes a Good MRI Agent? 1025.5.4 Health Issues with MRI Agents 1045.5.5 Texaphyrins 1045.6 Electron Paramagnetic Resonance Spectroscopy 1055.7 Lanthanides as Probes in Biological Systems 1056 Organometallic Chemistry of the Lanthanides 1106.1 Introduction 1106.2 The +3 Oxidation State 1106.2.1 Alkyls 1116.2.2 Aryls 1126.3 Cyclopentadienyls 1136.3.1 Compounds of the Unsubstituted Cyclopentadienyl Ligand (C5H5 = Cp; C5Me5 =Cp∗) 1136.3.2 Compounds [LnCp∗3] (Cp∗ = Pentamethylcyclopentadienyl) 1166.3.3 Bis(cyclopentadienyl) Alkyls and Aryls LnCp2R 1176.3.4 Bis(pentamethylcyclopentadienyl) Alkyls 1186.3.5 Hydride Complexes 1216.4 Cyclooctatetraene Dianion Complexes 1216.5 The +2 State 1226.5.1 Alkyls and Aryls 1226.5.2 Cyclopentadienyls 1236.5.3 Other Compounds 1266.6 The +4 State 1266.7 Metal–Arene Complexes 1286.8 Carbonyls 1296.9 Compounds with Lanthanide-Metal Bonds 1297 The Misfits: Scandium, Yttrium, and Promethium 1347.1 Introduction 1347.2 Scandium 1347.2.1 Binary Compounds of Scandium 1357.3 Coordination Compounds of Scandium 1367.3.1 The Aqua Ion and Hydrated Salts 1367.3.2 Other Complexes 1377.3.3 Alkoxides and Alkylamides 1397.3.4 Patterns in Coordination Number 1407.3.5 Scandium and Yttrium in the (+2) State 1447.4 Organometallic Compounds of Scandium 1457.5 Yttrium 1487.6 Promethium 1498 Introduction to the Actinides 1548.1 Introduction and Occurrence of the Actinides 1548.2 Synthesis 1558.3 Extraction of Th, Pa, and U 1578.3.1 Extraction of Thorium 1578.3.2 Extraction of Protactinium 1578.3.3 Extraction and Purification of Uranium 1578.3.4 Uranium Extraction from Seawater 1578.4 Uranium Isotope Separation 1598.4.1 Gaseous Diffusion 1598.4.2 Gas Centrifuge 1608.4.3 Electromagnetic Separation 1608.4.4 Laser Separation 1608.5 Characteristics of the Actinides 1608.6 Reduction Potentials of the Actinides 1628.7 Relativistic Effects 1639 Binary Compounds of the Actinides 1659.1 Introduction 1659.2 Halides 1659.2.1 Syntheses of the Halides 1679.2.2 Structure Types 1689.3 Thorium Halides 1709.4 Uranium Halides 1709.4.1 Uranium(VI) Compounds 1709.4.2 Uranium(V) Compounds 1729.4.3 Uranium(IV) Compounds 1729.4.4 Uranium(III) Compounds 1739.4.5 Uranium Hexafluoride and Isotope Separation 1739.5 Actinide Halides (Ac–Am) Excluding U and Th 1759.5.1 Actinium 1759.5.2 Protactinium 1759.5.3 Neptunium 1769.5.4 Plutonium 1779.5.5 Americium 1779.6 Halides of the Heavier Transactinides 1789.6.1 Curium(III) Chloride 1789.6.2 Californium(III) Chloride, Californium(III) Iodide, and Californium(II) Iodide 1789.6.3 Einsteinium(II) Chloride 1799.7 Oxides 1799.7.1 Thorium Oxide 1799.7.2 Uranium Oxides 1809.7.3 Plutonium Oxides 1809.8 Sulfides 1809.9 Uranium Hydride UH3 1819.10 Oxyhalides 18110 Coordination Chemistry of the Actinides 18410.1 Introduction 18410.2 General Patterns in the Coordination Chemistry of the Actinides 18510.3 Coordination Numbers in Actinide Complexes 18510.4 Types of Complex Formed 18710.5 Uranium and Thorium Chemistry 18710.5.1 Uranyl Complexes 18710.5.2 Coordination Numbers and Geometries in Uranyl Complexes 19010.5.3 Some Other Complexes 19210.5.4 Uranyl Nitrate and Its Complexes; Their Role in Processing Nuclear Waste 19310.5.5 Nuclear Waste Processing 19310.5.6 Uranium Oxo Complexes 19410.5.7 Uranium Nitrido Complexes 19510.5.8 Uranium(V) Complexes 19610.5.9 Uranium(III) Complexes 19710.5.10 Uranium(II) Complexes 19810.6 Complexes of the Actinide(IV) Nitrates and Halides 19910.6.1 Thorium Nitrate Complexes 19910.6.2 Uranium(IV) Nitrate Complexes 20010.6.3 Complexes of the Actinide(IV) Halides 20010.7 Thiocyanates 20210.8 Amides, Alkoxides, and Thiolates 20310.8.1 Amide Chemistry 20310.8.2 Alkoxides and Aryloxides 20710.8.3 Borohydrides 20910.8.4 Uranium Chelate Compounds 20910.9 Chemistry of Actinium 21010.10 Chemistry of Protactinium 21110.11 Chemistry of Neptunium 21210.11.1 Complexes of Neptunium 21310.12 Chemistry of Plutonium 21410.12.1 Aqueous Chemistry 21410.12.2 Stability of the Oxidation States of Plutonium 21510.12.3 Coordination Chemistry of Plutonium 21610.12.4 Plutonium in the Environment 21810.13 Chemistry of Americium and Subsequent Actinides 22010.13.1 Potentials 22010.14 Chemistry of the Later Actinides 22211 Electronic and Magnetic Properties of the Actinides 22811.1 Introduction 22811.2 Absorption Spectra 22911.2.1 Uranium (VI) – UO22+ – f0 22911.2.2 Uranium(V) – f1 23011.2.3 Uranium(IV) – f2 23011.2.4 Spectra of the Later Actinides 23311.3 Magnetic Properties 23411.3.1 Uranium Single Molecule Magnets 23612 Organometallic Chemistry of the Actinides 23812.1 Introduction 23812.2 Simple σ-Bonded Organometallics 23812.3 Cyclopentadienyls 24212.3.1 Oxidation State (VI) 24212.3.2 Oxidation State (V) 24212.3.3 Oxidation State (IV) 24212.3.4 Oxidation State (III) 24512.4 Compounds of the Pentamethylcyclopentadienyl Ligand (C5Me5 =Cp∗) 24612.4.1 Oxidation State (IV) 24612.4.2 Cationic Species and Catalysts 24712.4.3 Hydrides 24812.4.4 Oxidation State (III) 24912.4.5 Oxidation State (II) 24912.4.6 Some Recent Chemistry of Neptunium and Plutonium 25112.5 Tris(pentamethylcyclopentadienyl) Systems 25212.6 Other Metallacycles 25212.7 Cyclooctatetraene Dianion Compounds 25312.8 Arene Complexes 25412.8.1 Simple Arene Derivatives 25412.8.2 Arene-Supported Triazacyclononane Derivatives 25412.9 Carbonyls 25612.10 Compounds with Actinide-metal Bonds 25713 Synthesis of the Transactinides and Their Chemistry 26013.1 Introduction 26013.2 Finding New Elements 26113.3 Synthesis of the Transactinides 26113.4 Naming the Transactinides 26513.5 Predicting Electronic Arrangements 26613.6 Identifying the Elements 26613.7 Predicting Chemistry of the Transactinides 27213.8 What Is Known about the Chemistry of the Transactinides 27313.8.1 Element 104 27313.8.2 Element 105 27313.8.3 Element 106 27413.8.4 Element 107 27413.8.5 Element 108 27413.8.6 Elements 112 and 114 27613.9 And the Future? 276References 278Index 310