The course will be carried out through lectures and a series of exercises in which the concepts of group theory will be applied to the study of metallorganic molecules.
If lectures are given in a mixed or remote way, some changes may be introduced from what has been stated above, in order to comply with the programme envisaged and reported in the syllabus.
Storic development of organometalli chemistry. Classification of organometallics. Organometallics of main groups: synthetic procedures and reactivity. Applications of group theory in the rationalization of borane bonding. Organometallics of transition elements: Classification of ligands s-donor; Ligand s-donor/p-acceptor; ligand p-donor/p-acceptor. Group theory in the IR and Raman characterization of metallocarbonyls. Bonding in the organometallics using group theory: Symmetry and MO theory. Organometallics in catalysis: olefin hydrogenation, Monsanto cycle, Wacker cycle, olefin polymerization. Organometallics in the synthesis of film and nanoparticle materials. Organometallics in life sciences: toxicological aspects and application as therapeutic agents.
2) ORGANOMETAL COMPOUNDS OF MAIN GROUPS
- Preparation methods
- Organometallics of alkaline metals.
- Organometallics of alkaline earth metals and group 12: or Grignard and cyclopentadienyl group 2 reagents.
- Organometallics group 13: or alkyl- and aryl-aluminum; or carbo- and hydro-lighting. or Borani and carborani: rule of Wade, closo-, nido- and arachno-borani.
- Organometallic group 14: alkyl-Si, Ge, Pb. Silicones.
3) THE CHEMICAL BOND IN ORGANOMETAL COMPOUNDS
- Basic principles of group theory
- Derivation symmetry of a molecule.
- Character table interpretation.
- Exercise group theory
- Description of the bonding of simple systems such as the diboran (with SALC derivation).
- MO diagram of organometallic compounds with octahedral and tetrahedral symmetry.
4) ORGANOMETALLIC COMPOUNDS OF TRANSITION ELEMENTS
- Preparation methods
- sigma-donor ligands: alkyls, aryls.
- sigma-donor / pi-acceptor ligands: carbenes, carbines, alkylidines and alkylidines, carbonyls.
- pi-donor / pi-acceptor ligands: allyls, cyclopentadienyls, arenes.
- Exercise group theory:
- Derivation number of total modes in small molecules or derivation of IR bands for carbonyl metal systems.
- Active IR and Raman modes. o description of the bond by MO approach of bis-cyclopentadienyls symmetrically D5h and D5d.
5) APPLICATIVE AND INNOVATIVE ASPECTS
- Organometallic compounds in catalysis.
- Definition of the TON, TOF and EE parameters.
- Hydrogenation of olefins by Wilkinson catalyst and binding metathesis
- Acetic acid synthesis via Monsanto cycle.
- Synthesis of aldehydes by Wacker cycle.
- Olefin polymerization by heterogeneous catalysis (Ziegler-Natta polymerization notes).
- Homogeneous catalysis through constrained geometry catalyst.
- Organometallic compounds in the synthesis of materials:
- Application examples of organometallic compounds such as cyclopentadienyls and carbonyls in the preparation of materials in the form of films and nano particles.
- Organometallic compounds in life sciences:
- Toxicological issues.
- Organometallic compounds as therapeutic agents.
- Organometallic compounds as biosensors and for molecular recognition in aqueous solutions.
- Natural organometallic compounds: enzymes and proteins.
Lanthanides and rare-earth: unknown elements in everyday life.
Ch. Elschenbroich, "Organometallics", 3rd Edition, VCH, 2006.
Miessler, Tarr, Chimica Inorganica, 2011, Piccin (Chapters 4, 13, 14, 15).