PHD
  1. Inorganic chemistry  1.1. Coordination chemistry  1.1.1. Ligand field theory  1.1.2. Crystal field theory  1.1.3. Molecular Orbital Theory for Coordination Compounds  1.1.4. Stability of Coordination Compounds  1.1.5. Electronic spectra of coordination compounds  1.1.6. Isomerism in Coordination Compounds  1.1.7. Kinetics and mechanism of coordination reactions  1.2. Organometallic Chemistry  1.2.1. Metal Carbonyls  1.2.2. Metal alkyl and aryl  1.2.3. Fischer and Schrock carbonaceans  1.2.4. Oxidative Addition and Reductive Elimination  1.2.5. Metal Hydrides  1.2.6. Catalysis by organometallic compounds  1.2.7. Metallocenes and Sandwich Complexes  1.2.8. CH activation  1.3. Solid state chemistry  1.3.1. Crystal structures and lattices  1.3.2. Band theory and electrical properties  1.3.3. Defects in the crystal  1.3.4. Synthesis of solid state materials  1.3.5. Magnetic and optical properties of solids  1.3.6. Superconductivity  1.3.7. Solid state ionics  1.4. Bio-inorganic chemistry  1.4.1. Metalloproteins and enzymes  1.4.2. Metal ion transport and storage  1.4.3. The role of metals in medicine  1.4.4. Bioinspired catalysis  1.4.5. Metal–DNA interactions  1.4.6. Metal Complexes in Medical Science  1.5. Lanthanides and Actinides  1.5.1. Electronic configuration and oxidation states in lanthanides and actinides  1.5.2. Spectral and Magnetic Properties in Lanthanides and Actinides  1.5.3. Separation and Extraction of Lanthanides and Actinides  1.5.4. Coordination chemistry of f-block elements  1.6. Main Group Chemistry  1.6.1. Chemistry of boron compounds  1.6.2. Chemistry of Silicon and Germanium Compounds  1.6.3. Chemistry of Phosphorus and Sulfur Compounds  1.6.4. Organosilicon chemistry  1.6.5. Noble Gas Chemistry
  2. Organic chemistry  2.1. Reaction mechanism  2.1.1. Nucleophilic substitution reactions  2.1.2. Electrophilic addition and substitution reactions  2.1.3. Elimination reactions  2.1.4. Rearrangement reactions  2.1.5. Radical reactions  2.1.6. Pericyclic Reactions  2.1.7. Photochemical reactions  2.2. Stereoscopic  2.2.1. Chirality and optical activity  2.2.2. Structural analysis  2.2.3. Stereoelectronic effects  2.2.4. Asymmetric synthesis  2.2.5. Dynamic Stereochemistry  2.3. Organometallic Chemistry in Organic Synthesis  2.3.1. Organolithium and organomagnesium reagents  2.3.2. Transition metal catalyzed coupling reactions  2.3.3. Palladium-catalyzed reactions  2.3.4. Olefin Metathesis  2.3.5. Gold and silver catalysis  2.4. Natural products chemistry  2.4.1. Alkaloids and terpenoids  2.4.2. Steroids and Flavonoids  2.4.3. Total synthesis of natural products  2.4.4. Biosynthesis of natural products  2.5. Supramolecular Chemistry  2.5.1. Host-Guest Chemistry  2.5.2. Self-assembly and molecular recognition  2.5.3. Supramolecular Catalysis  2.5.4. Molecular Machines
  3. Physical Chemistry  3.1. Thermodynamics  3.1.1. Laws of Thermodynamics  3.1.2. Chemical Potential and Equilibrium  3.1.3. Statistical thermodynamics  3.1.4. Non-equilibrium thermodynamics  3.2. Quantum Chemistry  3.2.1. Schrödinger equation and its applications  3.2.2. Molecular orbital theory  3.2.3. Density functional theory  3.2.4. Post-Hartree–Fock methods  3.3. Chemical kinetics  3.3.1. Reaction rate theory  3.3.2. Mechanism and rate laws  3.3.3. Catalysis and enzyme kinetics  3.3.4. Reaction dynamics  3.4. Spectroscopy and molecular structure  3.4.1. Infrared Spectroscopy  3.4.2. UV-visible spectroscopy  3.4.3. Nuclear Magnetic Resonance Spectroscopy  3.4.4. Mass Spectrometry  3.4.5. Raman Spectroscopy  3.5. Surface and Colloid Chemistry  3.5.1. Absorption and Catalysis  3.5.2. Surfactants and micelles  3.5.3. Colloidal Stability  3.5.4. Nanomaterials and Interfaces
  4. Analytical chemistry  4.1. Chromatography  4.1.1. Gas Chromatography  4.1.2. High Performance Liquid Chromatography  4.1.3. Thin Layer Chromatography  4.1.4. Ion Chromatography  4.2. Electroanalytical techniques  4.2.1. Voltammetry and Polarography  4.2.2. Conductometry and potentiometry  4.2.3. Colometry  4.3. Spectroscopic Methods  4.3.1. Atomic absorption spectroscopy  4.3.2. Fluorescence Spectroscopy  4.3.3. X-ray diffraction  4.3.4. Electron paramagnetic resonance spectroscopy  4.4. Chemometrics  4.4.1. Data processing and statistical methods  4.4.2. Multidisciplinary analysis  4.4.3. Machine Learning in Analytical Chemistry
  5. Theoretical and Computational Chemistry  5.1. Molecular dynamics simulation  5.2. Quantum chemistry methods  5.3. Computational drug design  5.4. Machine Learning in Chemistry  5.5. Ab initio molecular dynamics
  6. Biophysics and Medicinal Chemistry  6.1. Drug discovery and design  6.2. Enzyme kinetics and inhibition  6.3. Chemical biology approach  6.4. Protein-ligand interactions  6.5. Bioorthogonal chemistry
  7. Materials chemistry  7.1. Polymer chemistry  7.1.1. Polymerization mechanism  7.1.2. Functional Polymers  7.1.3. Biodegradable Polymer  7.1.4. Conducting and semiconducting polymers  7.2. Nano Chemistry  7.2.1. Nanoparticles and nanostructures  7.2.2. Carbon-based nanomaterials  7.2.3. Quantum dots  7.3. Energy and Environmental Chemistry  7.3.1. Battery and Fuel Cell Chemistry  7.3.2. Green chemistry and sustainable materials  7.3.3. Photocatalysis

PHD → Inorganic chemistry → Lanthanides and Actinides ↓


Coordination chemistry of f-block elements


Introduction

The f-block elements, also called inner transition metals, include the lanthanides and actinides. These elements are typically characterized by filling the 4f and 5f orbitals, respectively. The coordination chemistry of these elements is fascinating because of their unique electronic configurations, oxidation states, and coordination numbers.

Lanthanides

The lanthanides include 15 elements with atomic numbers ranging from 57 (La) to 71 (Lu). These elements are known for their similar chemical properties, which arise from their partially filled 4f orbitals.

      
La - Lanthanum
Ce - Cerium
Pr - Praseodymium
Nd - Neodymium
Pm - Promethium
Sm - Samarium
Eu - Europium
Gd - Gadolinium
Tb - Terbium
Dy - Dysprosium
Ho - Holmium
Er - Erbium
Tm - Thulium
Yb - Ytterbium
Lu - Lutetium

Coordination compounds

Lanthanides form various coordination compounds, often exhibiting high coordination numbers due to their large ionic radii. They typically coordinate with oxygen, nitrogen, or sulfur donor atoms.

Example: Lanthanide nitrates

Lanthanide nitrates, such as Ln(NO3)3, often coordinate with water molecules, forming hydrates such as Ln(NO3)3·xH2O

Actinides

The actinides are a series of 15 elements, from actinium (Ac) to lawrencium (Lr), characterized by the gradual filling of the 5f orbitals. These elements are known for their radioactive properties and complex redox chemistry.

      
Ac - Actinium
Th - Thorium
Pa - Protactinium
U - Uranium
Np - Neptunium
Pu - Plutonium
Am - Americium
Cm - Curium
Bk - Berkelium
Cf - Californium
Es - Einsteinium
Fm - Fermium
Md - Mendelevium
No - Nobelium
Lr - Lawrencium

Coordination compounds

Actinides display diverse coordination chemistry due to their ability to reach multiple oxidation states. They often form complexes with oxygen and nitrogen donors.

Example: Uranium hexafluoride

A well-known actinide complex is uranium hexafluoride, UF6, which is used in uranium enrichment processes.

Electronic configuration

Understanding the electronic configuration of f-block elements is important for exploring their coordination chemistry. The general electronic configuration for lanthanides is [Xe] 4fn 6s2, and for actinides, it is [Rn] 5fn 7s2.

Lanthanide examples

      
La: [Xe] 5d1 6s2
Ce: [Xe] 4f1 5d1 6s2

Actinide examples

      
Th: [Rn] 6d2 7s2
U: [Rn] 5f3 6d1 7s2

Coordination numbers and geometry

The coordination number of a complex determines the number of donor atoms bonded to the central metal. Lanthanides typically display coordination numbers ranging from 8 to 12, reflecting their large size. In contrast, actinides typically display coordination numbers ranging from 6 to 10.

Geometry

The geometric arrangement of the ligands around the central metal can vary greatly:

  • Octahedral: coordination number 6, which is the same in both lanthanides and actinides.
  • Cubic: coordination number 8, often found in lanthanide complexes.
  • Trigonal bipyramidal: Less common but can be found in both lanthanide and actinide chemistry.

Chelation and multidentate ligands

The f-block elements often form stable complexes with multidentate ligands, which are ligands that can donate more than one electron pair to the central metal atom. These are known as chelating ligands.

EDTA complex

One of the most common chelating agents is ethylenediaminetetraacetic acid (EDTA), which forms strong complexes with both the lanthanides and actinides:

      
[Ln(EDTA)]- and [An(EDTA)]-

Stability of complexes

The stability of coordination compounds of f-block elements depends on several factors, including the size and charge of the metal ion, the type and charge of the ligand, and the solvent system.

Coordination chemistry applications

The coordination chemistry of the f-block elements is important for a variety of applications, ranging from materials science to medicine.

Medical imaging

Lanthanide complexes are used in MRI imaging due to their unique electronic properties.

Nuclear reactor

Actinide complexes are important in nuclear reactor design and fuel recycling protocols.

Conclusion

The coordination chemistry of f-block elements provides an insightful glimpse into the advanced principles of inorganic chemistry. Lanthanides and actinides, with their complex electronic configurations and various oxidation states, form a wide range of coordination compounds with unique geometries and properties.


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Coordination chemistry of f-block elements

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