Lanthanide and Actinide Chemistry (Inorganic Chemistry: A Textbook Series)

Cover
Title Page
Copyright Page
Contents
About the Author
Preface to the Second Edition
Preface to the First Edition
About the Companion Website
Chapter 1 Introduction to the Lanthanides
	1.1 Introduction
	1.2 Characteristics of the Lanthanides
	1.3 Occurrence and Abundance of the Lanthanides
	1.4 Lanthanide Ores
	1.5 Extracting and Separating the Lanthanides
		1.5.1 Extraction
		1.5.2 Separating the Lanthanides
	1.6 The Position of the Lanthanides in the Periodic Table
	1.7 The Lanthanide Contraction
	1.8 Recycling Lanthanides
	1.9 Isotopes
Chapter 2 The Lanthanides – Principles and Energetics
	2.1 Electron Configurations of the Lanthanides and f Orbitals
	2.2 What Do f Orbitals Look Like?
	2.3 How f Orbitals Affect Properties of the Lanthanides
	2.4 The Lanthanide Contraction
	2.5 Electron Configurations of the Lanthanide Elements and of Common Ions
	2.6 Patterns in Ionization Energies
	2.7 Atomic and Ionic Radii
	2.8 Patterns in Hydration Energies (Enthalpies) for the Lanthanide Ions
	2.9 Enthalpy Changes for the Formation of Simple Lanthanide Compounds
		2.9.1 Stability of Tetrahalides
		2.9.2 Stability of Dihalides
		2.9.3 Stability of Aqua Ions
	2.10 Patterns in Redox Potentials
Chapter 3 The Lanthanide Elements and Simple Binary Compounds
	3.1 Introduction
	3.2 The Elements
		3.2.1  Properties
		3.2.2  Synthesis
		3.2.3  Alloys and Uses of the Metals
	3.3 Binary Compounds
		3.3.1  Trihalides
		3.3.2  Tetrahalides
		3.3.3  Dihalides
		3.3.4  Oxides
	3.4 Borides
	3.5 Carbides
	3.6 Nitrides
	3.7 Hydrides
	3.8 Sulfides
Chapter 4 Coordination Chemistry of the Lanthanides
	4.1 Introduction
	4.2 Stability of Complexes
	4.3 Complexes
		4.3.1 The Aqua Ions
		4.3.2 Hydrated Salts
		4.3.3 Other O-Donors
		4.3.4 Complexes of β-Diketonates
		4.3.5 Lewis Base Adducts of β-Diketonate„ Complexes
		4.3.6 Nitrate and Carbonate Complexes
		4.3.7 Crown Ether Complexes
		4.3.8 Complexes of EDTA and Related Ligands
		4.3.9 Complexes of N-Donors
		4.3.10 Complexes of Porphyrins and Related Systems
		4.3.11 Halide Complexes
		4.3.12 Complexes of S-Donors
	4.4 Alkoxides, Alkylamides, and Related Substances
		4.4.1 Alkylamides
		4.4.2 Alkoxides
		4.4.3 Thiolates
		4.4.4 Borohydrides
	4.5 Coordination Numbers in Lanthanide Complexes
		4.5.1  General Principles
		4.5.2  Examples of the Coordination Numbers
		4.5.3  The Lanthanide Contraction and Coordination Numbers
		4.5.4  Formulae and Coordination Numbers
	4.6 The Coordination Chemistry of the +2 and +4 States
		4.6.1  The (+2) State
		4.6.2  The (+4) State
	4.7 Lanthanides in Living Systems
Chapter 5 Electronic and Magnetic Properties of the Lanthanides
	5.1 Magnetic and Spectroscopic Properties of the Ln3+ Ions
	5.2 Magnetic Properties of the Ln3+ Ions
		5.2.1 Adiabatic Demagnetization
		5.2.2 Single Molecule Magnets (SMMs) and Single Ion Magnets (SIMs)
	5.3 Energy-Level Diagrams for the Lanthanide Ions, and Their Electronic Spectra
		5.3.1 Electronic Spectra
		5.3.2 Hypersensitive Transitions
	5.4  Luminescence Spectra
		5.4.1 Quenching
		5.4.2 Antenna Effects
		5.4.3 Lanthanides in Upconversion
		5.4.4 Applications of Luminescence to Sensory Probes
			5.4.4.1 Terbium Luminescence to Detect Anthrax
			5.4.4.2 Fingerprint Detection
		5.4.5 Fluorescence and TV
		5.4.6 Lighting Applications
		5.4.7 Lasers
		5.4.8 Euro Banknotes
	5.5 NMR Applications
		5.5.1 β-Diketonates„ as NMR Shift Reagents
		5.5.2 Magnetic Resonance Imaging (MRI)
		5.5.3 What Makes a Good MRI Agent?
		5.5.4 Health Issues with MRI Agents
		5.5.5 Texaphyrins
	5.6 Electron Paramagnetic Resonance Spectroscopy
	5.7 Lanthanides as Probes in Biological Systems
Chapter 6 Organometallic Chemistry of the Lanthanides
	6.1 Introduction
	6.2 The +3 Oxidation State
		6.2.1  Alkyls
		6.2.2  Aryls
	6.3 Cyclopentadienyls
		6.3.1 Compounds of the Unsubstituted Cyclopentadienyl Ligand (C5H5 = Cp; C5Me5 = Cp*)
		6.3.2 Compounds [LnCp*3] •(Cp* = Pentamethylcyclopentadienyl)
		6.3.3 Bis(cyclopentadienyl) Alkyls and Aryls LnCp2R
		6.3.4 Bis(pentamethylcyclopentadienyl) Alkyls
		6.3.5 Hydride Complexes
	6.4 Cyclooctatetraene Dianion Complexes
	6.5 The +2 State
		6.5.1  Alkyls and Aryls
		6.5.2  Cyclopentadienyls
		6.5.3  Other Compounds
	6.6 The +4 State
	6.7 Metal–Arene Complexes
	6.8 Carbonyls
	6.9 Compounds with Lanthanide-Metal Bonds
Chapter 7 The Misfits: Scandium, Yttrium, and Promethium
	7.1 Introduction
	7.2 Scandium
		7.2.1 Binary Compounds of Scandium
	7.3 Coordination Compounds of Scandium
		7.3.1 The Aqua Ion and Hydrated Salts
		7.3.2 Other Complexes
		7.3.3 Alkoxides and Alkylamides
		7.3.4 Patterns in Coordination Number
		7.3.5 Scandium and Yttrium in the (+2) State
	7.4 Organometallic Compounds of Scandium
	7.5 Yttrium
	7.6 Promethium
Chapter 8 Introduction to the Actinides
	8.1 Introduction and Occurrence of the Actinides
	8.2 Synthesis
	8.3 Extraction of Th, Pa, and U
		8.3.1 Extraction of Thorium
		8.3.2 Extraction of Protactinium
		8.3.3 Extraction and Purification of Uranium
		8.3.4 Uranium Extraction from Seawater
	8.4 Uranium Isotope Separation
		8.4.1 Gaseous Diffusion
		8.4.2 Gas Centrifuge
		8.4.3 Electromagnetic Separation
		8.4.4 Laser Separation
	8.5 Characteristics of the Actinides
	8.6 Reduction Potentials of the Actinides
	8.7 Relativistic Effects
Chapter 9 Binary Compounds of the Actinides
	9.1 Introduction
	9.2 Halides
		9.2.1 Syntheses of the Halides
		9.2.2 Structure Types
	9.3 Thorium Halides
	9.4 Uranium Halides
		9.4.1 Uranium(VI) Compounds
		9.4.2 Uranium(V) Compounds
		9.4.3 Uranium(IV) Compounds
		9.4.4 Uranium(III) Compounds
		9.4.5 Uranium Hexafluoride and Isotope Separation
	9.5 Actinide Halides (Ac–Am) Excluding U and Th
		9.5.1 Actinium
		9.5.2 Protactinium
		9.5.3 Neptunium
		9.5.4 Plutonium
		9.5.5 Americium
	9.6 Halides of the Heavier Transactinides
		9.6.1 Curium(III) Chloride
		9.6.2 Californium(III) Chloride, Californium(III) Iodide, and Californium(II) Iodide
		9.6.3 Einsteinium(II) Chloride
	9.7 Oxides
		9.7.1 Thorium Oxide
		9.7.2 Uranium Oxides
		9.7.3 Plutonium Oxides
	9.8 Sulfides
	9.9 Uranium Hydride UH3
	9.10 Oxyhalides
Chapter 10 Coordination Chemistry of the Actinides
	10.1 Introduction
	10.2 General Patterns in the Coordination Chemistry of the Actinides
	10.3 Coordination Numbers in Actinide Complexes
	10.4 Types of Complex Formed
	10.5 Uranium and Thorium Chemistry
		10.5.1 Uranyl Complexes
		10.5.2 Coordination Numbers and Geometries in Uranyl Complexes
		10.5.3 Some Other Complexes
		10.5.4 Uranyl Nitrate and Its Complexes; Their Role in Processing Nuclear Waste
		10.5.5 Nuclear Waste Processing
		10.5.6 Uranium Oxo Complexes
		10.5.7 Uranium Nitrido Complexes
		10.5.8 Uranium(V) Complexes
		10.5.9 Uranium(III) Complexes
		10.5.10 Uranium(II) Complexes
	10.6 Complexes of the •Actinide•(•IV) Nitrates and Halides
		10.6.1  Thorium Nitrate Complexes
		10.6.2  Uranium(IV) Nitrate Complexes
		10.6.3  Complexes of the „Actinide„(„IV) Halides
	10.7 Thiocyanates
	10.8 Amides, Alkoxides, and Thiolates
		10.8.1 Amide Chemistry
		10.8.2 Alkoxides and Aryloxides
		10.8.3 Borohydrides
		10.8.4 Uranium Chelate Compounds
	10.9 Chemistry of Actinium
	10.10 Chemistry of Protactinium
	10.11 Chemistry of Neptunium
		10.11.1 Complexes of Neptunium
	10.12 Chemistry of Plutonium
		10.12.1 Aqueous Chemistry
		10.12.2 Stability of the Oxidation States of Plutonium
		10.12.3 Coordination Chemistry of Plutonium
		10.12.4 Plutonium in the Environment
	10.13 Chemistry of Americium and Subsequent Actinides
		10.13.1 Potentials
	10.14 Chemistry of the Later Actinides
Chapter 11 Electronic and Magnetic Properties of the Actinides
	11.1 Introduction
	11.2 Absorption Spectra
		11.2.1 Uranium (VI) – UO22+ – f0
		11.2.2 Uranium(V) – f1
		11.2.3 Uranium(IV) – f2
		11.2.4 Spectra of the Later Actinides
	11.3 Magnetic Properties
		11.3.1  Uranium Single Molecule Magnets
Chapter 12 Organometallic Chemistry of the Actinides
	12.1 Introduction
	12.2 Simple σ-Bonded„ Organometallics
	12.3 Cyclopentadienyls
		12.3.1 Oxidation State •(VI)
		12.3.2 Oxidation State •(V)
		12.3.3 Oxidation State •(IV)
		12.3.4 Oxidation State •(III)
	12.4 Compounds of the Pentamethylcyclopentadienyl Ligand (C5Me5 = Cp*)
		12.4.1 Oxidation State (IV)
		12.4.2 Cationic Species and Catalysts
		12.4.3 Hydrides
		12.4.4 Oxidation State •(III)
		12.4.5 Oxidation State •(II)
		12.4.6 Some Recent Chemistry of Neptunium and Plutonium
	12.5 Tris(pentamethylcyclopentadienyl) Systems
	12.6 Other Metallacycles
	12.7 Cyclooctatetraene Dianion Compounds
	12.8 Arene Complexes
		12.8.1 Simple Arene Derivatives
		12.8.2 Arene-Supported Triazacyclononane Derivatives
	12.9 Carbonyls
	12.10 Compounds with Actinide-metal Bonds
Chapter 13 Synthesis of the Transactinides and Their Chemistry
	13.1 Introduction
	13.2 Finding New Elements
	13.3 Synthesis of the Transactinides
	13.4 Naming the Transactinides
	13.5 Predicting Electronic Arrangements
	13.6 Identifying the Elements
	13.7 Predicting Chemistry of the Transactinides
	13.8 What Is Known about the Chemistry of the Transactinides
		13.8.1 Element 104
		13.8.2 Element 105
		13.8.3 Element 106
		13.8.4 Element 107
		13.8.5 Element 108
		13.8.6 Elements 112 and 114
	13.9 And the Future?
References
Index
EULA