Cotton S. Lanthanide and Actinide Chemistry

Wiley, 2006. — 280 p. — (Inorganic Chemistry - A Textbook Series)Characteristics of the Lanthanides
The Occurrence and Abundance of the Lanthanides
Lanthanide Ores
Extracting and Separating the Lanthanides
Extraction
Separating the Lanthanides
The Position of the Lanthanides in the Periodic Table
The Lanthanide Contraction
The Lanthanides – Principles and Energetics
Electron Configurations of the Lanthanides and f Orbitals
What do f Orbitals Look Like?
How f Orbitals affect Properties of the Lanthanides
The Lanthanide Contraction
Electron Configurations of the Lanthanide Elements and of Common Ions
Patterns in Ionization Energies
Atomic and Ionic Radii
Patterns in Hydration Energies (Enthalpies) for the Lanthanide Ions
Enthalpy Changes for the Formation of Simple Lanthanide Compounds
Stability of Tetrahalides
Stability of Dihalides
Stability of Aqua Ions
Patterns in Redox Potentials
The Lanthanide Elements and Simple Binary Compounds
ntroduction
The Elements
Properties
Synthesis
Alloys and Uses of the Metals
Binary Compounds
Trihalides
Tetrahalides
Dihalides
OxidesBorides
Carbides
Nitrides
Hydrides
Sulfides
Coordination Chemistry of the LanthanidesStability of Complexes
Complexes
The Aqua Ions
Hydrated Salts
Other O-Donors
Complexes of β-Diketonates
Lewis Base Adducts of β-Diketonate Complexes
Nitrate Complexes
Crown Ether Complexes
Complexes of EDTA and Related Ligands
Complexes of N-Donors
Complexes of Porphyrins and Related Systems
Halide Complexes
Complexes of S-Donors
Alkoxides, Alkylamides and Related Substances
Alkylamides
Alkoxides
Thiolates
Coordination Numbers in Lanthanide Complexes
General Principles
Examples of the Coordination Numbers
The Lanthanide Contraction and Coordination Numbers
Formulae and Coordination Numbers
The Coordination Chemistry of the +2 and +4 States
The (+2) State
The (+4) State
Electronic and Magnetic Properties of the Lanthanides
Magnetic and Spectroscopic Properties of the Ln3+ Ions
Magnetic Properties of the Ln3+ Ions
Adiabatic Demagnetization
Energy Level Diagrams for the Lanthanide Ions, and their
Electronic Spectra
Electronic Spectra
Hypersensitive Transitions
Luminescence Spectra
Quenching
Antenna Effects
Applications of Luminescence to Sensory Probes
Fluorescence and TV
Lighting Applications
Contents xi
Lasers
Euro Banknotes
NMR Applications
β-Diketonates as NMR Shift Reagents
Magnetic Resonance Imaging (MRI)
What Makes a Good MRI Agent?
Texaphyrins
Electron Paramagnetic Resonance Spectroscopy
Lanthanides as Probes in Biological Systems
Organometallic Chemistry of the Lanthanides
ntroduction
The +3 Oxidation State
Alkyls
Aryls
Cyclopentadienyls
Compounds of the Unsubstituted Cyclopentadienyl Ligand
(C5H5 = Cp; C5Me5 = Cp*)
Compounds [LnCp*3] (Cp* = Pentamethylcyclopentadienyl)
Bis(cyclopentadienyl) Alkyls and Aryls LnCp2R
Bis(pentamethylcyclopentadienyl) Alkyls
Hydride Complexes
Cyclooctatetraene Dianion Complexes
The +2 State
Alkyls and Aryls
Cyclopentadienyls
Other Compounds
The +4 State
Metal–Arene Complexes
Carbonyls
The Misfits: Scandium, Yttrium, and Promethium
ntroduction
Scandium
Binary Compounds of Scandium
Coordination Compounds of Scandium
The Aqua Ion and Hydrated Salts
Other Complexes
Alkoxides and Alkylamides
Patterns in Coordination Number
Organometallic Compounds of Scandium
Yttrium
Promethium
The Lanthanides and Scandium in Organic Chemistry
ntroduction
Cerium(IV) Compounds
Oxidation of Aromatics
Oxidation of Alkenes
Oxidation of AlcoholsSamarium(II) Iodide, SmI
Reduction of Halogen Compounds
Reduction of α-Heterosubstituted Ketones
Reductions of Carbonyl Groups
Barbier Reactions
Reformatsky Reactions
Lanthanide β-Diketonates as Diels–Alder Catalysts
Hetero-Diels–Alder Reactions
Cerium(III) Chloride and Organocerium Compounds
Cerium(III) Chloride and Metal Hydrides
Scandium Triflate and Lanthanide Triflates
Friedel–Crafts Reactions
Diels–Alder Reactions
Mannich Reactions
mino-Diels–Alder Reactions
Alkoxides and Aryloxides
Lanthanide Metals
Organometallics and Catalysis
ntroduction to the Actinides
ntroduction and Occurrence of the Actinides
Synthesis
Extraction of Th, Pa, and U
Extraction of Thorium
Extraction of Protactinium
Extraction and Purification of Uranium
Uranium Isotope Separation
Gaseous Diffusion
Gas Centrifuge
Electromagnetic Separation
Laser Separation
Characteristics of the Actinides
Reduction Potentials of the Actinides
Relativistic Effects
Binary Compounds of the Actinides
ntroduction
Halides
Syntheses
Structure Types
Thorium Halides
Uranium Halides
Uranium(VI) Compounds
Uranium(V) Compounds
Uranium (IV) Compounds
Uranium(III) Compounds
Uranium Hexafluoride and Isotope Separation
Contents xiii
The Actinide Halides (Ac–Am) excluding U and Th
Actinium
Protactinium
Neptunium
Plutonium
Americium
Halides of the Heavier Transactinides
Curium(III) Chloride
Californium(III) Chloride, Californium(III) Iodide, and Californium(II) Iodide
Einsteinium(III) Chloride
Oxides
Thorium Oxide
Uranium Oxides
Uranium Hydride UH
Oxyhalides
Coordination Chemistry of the Actinides
ntroduction
General Patterns in the Coordination Chemistry of the Actinides
Coordination Numbers in Actinide Complexes
Types of Complex Formed
Uranium and Thorium Chemistry
Uranyl Complexes
Coordination Numbers and Geometries in Uranyl Complexes
Some Other Complexes
Uranyl Nitrate and its Complexes; their Role in Processing Nuclear Waste
Nuclear Waste Processing
Complexes of the Actinide(IV) Nitrates and Halides
Thorium Nitrate Complexes
Uranium(IV) Nitrate Complexes
Complexes of the Actinide(IV) Halides
Thiocyanates
Amides, Alkoxides and Thiolates
Amide Chemistry
Alkoxides and Aryloxides
Chemistry of Actinium
Chemistry of Protactinium
Chemistry of Neptunium
Complexes of Neptunium
Chemistry of Plutonium
Aqueous Chemistry
The Stability of the Oxidation States of Plutonium
Coordination Chemistry of Plutonium
Plutonium in the Environment
Chemistry of Americium and Subsequent Actinides
Potentials
Chemistry of the Later ActinidesElectronic and Magnetic Properties of the Actinides
ntroduction
Absorption Spectra
Uranium(VI) – UO
+ – f
Uranium(V) – f
Uranium(IV) – f
Spectra of the Later Actinides
Magnetic Properties
Organometallic Chemistry of the Actinides
ntroduction
Simple σ-Bonded Organometallics
Cyclopentadienyls
Oxidation State (VI)
Oxidation State (V)
Oxidation State (IV)
Oxidation State (III)
Compounds of the Pentamethylcyclopentadienyl Ligand (C5Me5 = Cp*)
Oxidation State(IV)
Cationic Species and Catalysts
Hydrides
Oxidation State (III)
Tris(pentamethylcyclopentadienyl) Systems
Other Metallacycles
Cyclooctatetraene Dianion Compounds
Arene Complexes
Carbonyls
Synthesis of the Transactinides and their Chemistry
ntroduction
Finding New Elements
Synthesis of the Transactinides
Naming the Transactinides
Predicting Electronic Arrangements
dentifying the Elements
Predicting Chemistry of the Transactinides
What is known about the Chemistry of the Transactinides
Element
Element
Element
Element
Element
And the Future?