Learning objectives
Knowledge: educate students on the basic concepts of organometallic chemistry with particular emphasis to the synthesis, structure and reactivity of the main classes of organometallic compounds.
Comprehension ability: the students are prompted to use all the concepts acquired from the course program in order to understand the chemical features and behaviour of a given organometallic entuty, embedding them with other knowledge deriving from other courses, such as Inorganic and Organic Chemistry.
Prerequisites
Knowledge of the fundamental concepts of inorganic, organic and coordination chemistry
Course unit content
Review of some basic knowledge of coordination chemistry (metal-ligand bonding, coordination geometries, chelation).
Metal-carbon interaction based on the type of C-ligand (sigma-donor, sigma-donor/pi-acceptor, pi-donor/pi-acceptor), 18e rule.
Organometallic chemistry of some s and p-blocks metals: organolithium compounds, organomagnesium compounds, organoalluminium compounds, organisilicon compounds, organophosphorious compounds.
Sistematic study of the main classes of C-based ligands for transition metals: alkyls and aryls, carbonyls, monoolefins, dienes, allens, alkynes, cyclopentadienyls, arenes, carbenes, isonitriles.
Agostic interactions, beta-elimination, alfa-elimination.
Substitution reaction is octahedral and square-planar complexes.
Nucleophilic and electrophilic addition reactions to coordinated ligands.
Oxidative addition, migratory insertion, reductive elimination.
Organometallic catalysis:main differences between homogeneous and heterogeneous catalysis, role played by an organometallic catalyst (ligand and metal effect), efficiency of a catalyst. Homogeneous hydrogenation, hydrogen transfer recation, hydroformilation, coupling reactions (Heck, Suzuki, Sonogashira, Negishi), nucleophilic addition on coordinated allenes.
Full programme
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Bibliography
- The Organometallic Chemistry of the Transition Metals, Robert H. Crabtree Wiley
- Organometallics, A Coincise Introduction, Ch. Elschenbroich, A. Salzer Wiley-VCH
- Fundamentals of Organometallic Chemistry, Steinborn D., Wiley-VCH
Teaching methods
Oral lessons (48 hours)
Assessment methods and criteria
Learning of the basic concepts of organometallic chemistry, with particular emphasis to the ligant to metal electroni donation and metal to ligand back-donation, in order to understand the different reactivity shown by a free ligand (not coordinated organic molecule) and metal-bound organic molecule. Analysis of the effect played by all the actors involved in the reaction that's, type of organic ligand, substituents directly attached to the C-atoms bound to the metal, type of metal (its position in the Periodic Table and its electronegativity), type of ancillary (spectators) ligands. Definition of a possible synthetic strategy for the preparation of simple organometallic compounds, taking into consideration the type of ligand, metal and experimental conditions (temperatrure, solvent) required for getting the requested moleculra structure and chemical reactivity. Ability to rationalize the most convinient spectroscopic and analytical tecniques for the characterization of a given organometallic compounds. Ability to use the acquired concepts in order to understand some catalytic mechanisms governing some useful metal-catalysed organic syntehses.
Other information
The slides of the lessons are available on the web. The teacher is available for tutoring (upon agreement).
