Lanthanide and Actinide Chemistry by Simon Cotton (informative)
Free download Lanthanide and Actinide Chemistry by Simon Cotton
Authors of: Lanthanide and Actinide Chemistry by Simon Cotton
Simon Cotton
Table of Contents in Lanthanide and Actinide Chemistry by Simon Cotton
Preface
1 Introduction to the Lanthanides
1.1 Introduction
1.2 Characteristics of the Lanthanides
1.3 The 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
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
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
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 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
4.5 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
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
5.3 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 Applications of Luminescence to Sensory Probes
5.4.4 Fluorescence and TV
5.4.5 Lighting Applications
5.4.6 Lasers
5.4.7 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 Texaphyrins
5.6 Electron Paramagnetic Resonance Spectroscopy
5.7 Lanthanides as Probes in Biological Systems
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
6.3.2 Compounds [LnCp*3]
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
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
7.4 Organometallic Compounds of Scandium
7.5 Yttrium
7.6 Promethium
8 The Lanthanides and Scandium in Organic Chemistry
8.1 Introduction
8.2 Cerium(IV) Compounds
8.2.1 Oxidation of Aromatics
8.2.2 Oxidation of Alkenes
8.2.3 Oxidation of Alcohols
8.3 Samarium(II) Iodide, SmI2
8.3.1 Reduction of Halogen Compounds
8.3.2 Reduction of α-Heterosubstituted Ketones
8.3.3 Reductions of Carbonyl Groups
8.3.4 Barbier Reactions
8.3.5 Reformatsky Reactions
8.4 Lanthanide β-Diketonates as Diels–Alder Catalysts
8.4.1 Hetero-Diels–Alder Reactions
8.5 Cerium(III) Chloride and Organocerium Compounds
8.6 Cerium(III) Chloride and Metal Hydrides
8.7 Scandium Triflate and Lanthanide Triflates
8.7.1 Friedel–Crafts Reactions
8.7.2 Diels–Alder Reactions
8.7.3 Mannich Reactions
8.7.4 Imino-Diels–Alder Reactions
8.8 Alkoxides and Aryloxides
8.9 Lanthanide Metals
8.10 Organometallics and Catalysis
9 Introduction to the Actinides
9.1 Introduction and Occurrence of the Actinides
9.2 Synthesis
9.3 Extraction of Th, Pa, and U
9.3.1 Extraction of Thorium
9.3.2 Extraction of Protactinium
9.3.3 Extraction and Purification of Uranium
9.4 Uranium Isotope Separation
9.4.1 Gaseous Diffusion
9.4.2 Gas Centrifuge
9.4.3 Electromagnetic Separation
9.4.4 Laser Separation
9.5 Characteristics of the Actinides
9.6 Reduction Potentials of the Actinides
9.7 Relativistic Effects
10 Binary Compounds of the Actinides
10.1 Introduction
10.2 Halides
10.2.1 Syntheses
10.2.2 Structure Types
10.3 Thorium Halides
10.4 Uranium Halides
10.4.1 Uranium(VI) Compounds
10.4.2 Uranium(V) Compounds
10.4.3 Uranium (IV) Compounds
10.4.4 Uranium(III) Compounds
10.4.5 Uranium Hexafluoride and Isotope Separation
10.5 The Actinide Halides (Ac–Am) excluding U and Th
10.5.1 Actinium
10.5.2 Protactinium
10.5.3 Neptunium
10.5.4 Plutonium
10.5.5 Americium
10.6 Halides of the Heavier Transactinides
10.6.1 Curium(III) Chloride
10.6.2 Californium(III
) Chloride
10.6.3 Lawrencium(III) Chloride
10.7 Dioxides of the Actinides
10.8 Carbides
10.9 Nitrides
10.10 Phosphides
10.11 Hydrides
11 Coordination Chemistry of the Actinides
11.1 Introduction
11.2 Actinyl(V) Ions
11.3 Actinyl(VI) Ions
11.4 Transuranium(VI) Actinyl Complexes
11.5 Compounds of Th(IV) and U(IV)
11.6 Coordination Numbers of the Actinides
11.7 Actinide Macrocyclic Complexes
11.8 Chelating Ligands and Crown Ethers
12 Organometallic Chemistry of the Actinides
12.1 Introduction
12.2 Actinide–Cyclopentadienyl Complexes
12.3 Uranyl–Cyclopentadienyl Complexes
12.4 Thorium and Uranium Cyclopentadienyl Complexes
12.5 Tetravalent Actinide Metallocenes
12.6 Actinide Carbonyl Complexes
12.7 Cyclooctatetraene Complexes
12.8 Organometallics of Th, Pa, U, and Np
12.8.1 Actinide–Carbon Bond Formation
12.8.2 Organometallic Compounds in Catalysis
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