METALORGANIC AND COORDINATION CHEMISTRY
Learning outcomes of the course unit
To give an overview of the most important classes of organometallic compounds in temrs of structure, synthesis and reactivity, together with the discussion of the most important and typical organometallic catalyses
Knowledge of the basic concepts of coordination chemistry and spectroscopy (IR and NMR)
Course contents summary
Quick review of the main aspects of coordination chemistry (donor-acceptor systems, crystal-field theory, ligand-field theory, magnetism of the complexes, trans-effect and trans-influence)
Ligand-to-metal donation and metal-to-ligand backdonation (sigma-donor ligands, sigma-donor/pi-acceptor ligands, pi-donor/pi-acceptor ligands). 18 electrons valence rule, coordinatively saturated or unsaturated metal-complexes.
Systematic study of the main classes of organometallic ligands: hydrides, phosphines, alkyls and aryls, carbonyls, mono-olefines, dienes and allyls, alkynes, cyclopentadienes and arenes, carbenes, isonitriles
Alfa-agostic interaction, alfa-abstraction, beta-elimination
Substitution reactions on octahedral complexes and square-planar complexes; dissociative mechanism, associative interchange mechanism, dissociative interchange mechanism, dissociative mechanism
Nucleophilic and electrophilic addition to coordinated ligands (CO, olefins, arenes, cyclopentadienes, dienes, allyls), Davies-Green-Mingos rules
Oxidative addition, migratory insertion, reductive elimination (reaction mechanisms)
Metallorganic catalysis: differences between homogeneous and heterogeneous catalysis. Role of the metallorganic catalyst. Efficiency and selectivity of a catalyst (ton and tof parameters, chemoselctivity, regioselectivity, stereoselectivity). Homogeneous hydrogenation, hydrogen transfer, hydroformilation, carbonylation of methanol (Monsanto and Cativa processes), olefin metathesis, coupling reactions (Heck, Suzuki, Sonogashira), polymerization of olefins (Ziegler-Natta and metallocene-catalysts)
- Robert H. Crabtree, "The Organometallic Chemistry of the Transition Metals", Fifth Edition, Wiley Ed.
- Ch. Eilschenbroich, A. Salzer, "Organometallics, A Coincive Introduction", VCH Ed.