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 → Organometallic Chemistry ↓


Metal alkyl and aryl


Metal alkyls and aryls are an essential part of organometallic chemistry, which itself is a fascinating field at the intersection of organic and inorganic chemistry. Organometallic compounds are characterized by a metal-carbon bond. In the case of metal alkyls and aryls, these compounds involve metals bound to alkyl or aryl groups. Understanding these compounds requires looking at both their structures and their chemical behavior.

Introduction to metal alkyls and aryls

By definition, organometallic compounds typically contain at least one carbon-to-metal chemical bond. Metal alkyls and aryls are specific types of these compounds, where the metal is bonded to an alkyl group (CnH2n+1) or aryl group (derivatives of benzene and similar aromatic rings). These compounds are fundamental to catalysis, the synthesis of organic compounds, and materials science, among other applications.

Chemical structure of metal alkyl and aryl

The structure of a metal alkyl or aryl compound involves a metal atom or ion directly attached to a carbon atom within the alkyl or aryl group. This bond formation involves the overlap of orbitals. Depending on the metal and the attached group, the nature of the bond may involve σ-bonds or π-bonds.

        R M
Here, R represents the alkyl or aryl group, and M represents the metal. This simple notation can represent different structures depending on the specific metal and group:

  • For metal alkyls: Me-M, where Me represents a methyl group (CH3).
  • For metal aryls: Ph-M, where Ph stands for phenyl group (C6H5).

Visual example

Here is an illustration of a simple metal alkyl compound that has a methyl group attached to a metal:

CH3 M

And here's an example of a metal aryl compound containing a phenyl group:

Ph M

Relationships and sustainability

The metal-carbon bond in metal alkyls and aryls can be polarized due to the difference in electronegativities between the metal and carbon. Generally, metals are more electropositive, leading to a partial positive charge in the metal and a partial negative charge in the carbon. This polarity significantly affects the stability and reactivity of these compounds.

Transition metals often form strong covalent bonds with carbon in metal alkyls and aryls. The d-orbitals of transition metals play an important role in forming π-bonds with carbon, increasing the stability of these bonds. Main group metals, such as zinc or aluminum, usually show more ionic character in their metal-carbon bonds.

Reactivity of metal alkyls and aryls

The reactivity of metal alkyls and aryls depends largely on the electronic environment created by the metal and the supporting ligand. Here are some of the reactions in which metal alkyls and aryls commonly participate:

  • Insertion reactions: It involves the insertion of small molecules such as CO or alkene into the metal-carbon bond.
  • Oxidative addition: The oxidation state at the metal centre increases while simultaneously new bonds are formed with additional incoming atoms.
  • Reductive elimination: This is the opposite of oxidative addition, where the metal reduces its oxidation state by eliminating a fragment which becomes a stable molecule.

Synthesis of metal alkyls and aryls

The synthesis of metal alkyls and aryls can be carried out via several routes, each optimized for the specific metals and required functionalities:

  1. Alkylation with Grignard reagents: Grignard reagents react with metal halides to form metal alkyls.
                Rmgx + Mxn → Rm + (n)mgx2
  2. Transmetalation: A metal halide exchanges with another metal alkyl to yield a new metal alkyl compound.
                RAG + MX → RM + AGX

Applications in industry and research

Metal alkyls and aryls play an important role in the development of modern chemical processes. Here are the notable applications:

  • Catalysis: Metals serve as catalysts or catalytic precursors in reactions such as alkyl and aryl polymerizations and hydrogenations.
  • Organic synthesis: Used to efficiently form carbon–carbon and carbon–heteroatom bonds.
  • Materials science: Employed in the preparation of thin films and nano materials through vapor deposition methods.

Conclusion

Metal alkyls and aryls represent an important area in organometallic chemistry, which combines concepts from both the inorganic and organic fields. Their unique structure and reactivity profile have opened up many industrial applications and advanced research into catalytic processes. Understanding their behavior and synthesis routes remains important in exploring new scientific frontiers and optimizing existing chemical methodology.


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Metal alkyl and aryl

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