Organometallic chemistry
Graduate · Chemistry
Syllabus focus
Theoretical / proof-based
Pricing
Graduate-level rates are set on consultation. See the pricing page for K–12 and undergraduate rates.
Topics typically covered
Theoretical / proof-based
Electronic structure and bonding
- 18-electron rule: rigorous application and exceptions
- Tolman electronic parameters and ligand effects
- Dewar–Chatt–Duncanson model for metal–alkene bonding
- Agostic interactions and three-center two-electron bonds
- Metal–ligand multiple bonds: carbenes, carbynes, nitrides
- Oxidation state formalism vs covalent bond classification
- Electron counting in clusters and metal–metal bonded systems
- Fluxionality and NMR timescales in organometallics
- Redox non-innocent ligands
- Computational analysis of organometallic bonding
Fundamental reaction steps
- Oxidative addition: concerted vs stepwise mechanisms
- Reductive elimination: stereochemistry and rate laws
- Migratory insertion: regio- and stereoselectivity
- β-Hydride elimination and its suppression strategies
- Nucleophilic and electrophilic attack on coordinated ligands
- Ligand substitution: associative, dissociative, and interchange
- Trans effect and trans influence in synthesis planning
- C–H activation mechanisms: oxidative addition vs σ-bond metathesis
- Metal–ligand cooperation and bifunctional catalysis
- Electron transfer in organometallic catalysis
Catalytic cycles
- Cross-coupling: Pd, Ni, Cu catalytic cycles in detail
- Olefin metathesis: Chauvin mechanism and catalyst decomposition
- Hydroformylation: rhodium and cobalt cycle comparisons
- Asymmetric hydrogenation: Wilkinson, Noyori, and chiral ligands
- C–H borylation and silylation mechanisms
- Carbonylation and hydroacylation cycles
- Polymerization: Cossee–Arlman and metallocene mechanisms
- Pauson–Khand and cycloaddition catalysis
- Photoredox organometallic catalysis
- Mechanistic studies: kinetics, isotope effects, intermediate trapping
Advanced topics
- Supported organometallic catalysts and surface science
- Biomimetic organometallic chemistry
- Frustrated Lewis pairs and main-group alternatives
- Small molecule activation: N₂, CO₂, H₂O
- Organometallic photochemistry
- Electrochemistry of organometallic complexes
- Air-sensitive synthesis and characterization techniques
- Scale-up and process chemistry of catalytic reactions
- Intellectual property in catalyst and ligand design
- Literature analysis of controversial mechanistic proposals
Notes
Graduate-level organometallic chemistry for PhD and advanced MS students. Topics reflect common organometallic chemistry syllabi at US research universities. Prior undergraduate inorganic and organic chemistry required.