CHIMICA ORGANOMETALLICA

The aim of the course is to acquire basic knowledge on organometallic compounds of metals of the main groups and of transition metals with particular reference to synthetic procedures, their properties, and reactivity. The course also aims to provide students with knowledge relating to the application of organometallic compounds in modern chemistry: application in homogeneous catalysis, in the synthesis of materials, and in life sciences.

• Knowledge and understanding: Base knowledge of organometallics: synthetic procedure and properties. Importance of organometallics in today’s chemistry: applications of OM complexes in catalysis, materials science and life science.
• Applying knowledge and understanding: Ability to apply what students have learned during the lectures on the group theory exercises.
• Making judgments:  Students learn to evaluate in an objective way what they have learned. 
• Communication skills: Students acquire communication skills that are formed both during lectures and the exercise activity thanks to a continuous verbal dialogue with the teacher, and furthermore during the oral exam. 
• Learning skills: Learning skills are assessed through oral examination and exercises that are an important part of the course.

 Information for students with disabilities and/or SLD

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.

Attendance of lessons is required in accordance with the regulations of the CdS.

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.

SEMINAR ACTIVITIES

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).

Oral exams on the topics of the course with exercises on the application of group theory.

Verification of learning can also be carried out electronically, should the conditions require it.

Link exam calendar: https://www.dsc.unict.it/corsi/lm-54-sc/esami?aa=123

Typical questions

- Description of the organometallic compounds of group I.

- Grignard's reagents.

- Insertion-migratory reactions: reaction mechanism.

- Types of ligands.

- Carbenes and Fischer carbines.

- Alkylidenes and Schrock alkylidines.

- Catalysis: Monsanto cycle.

- Hydrogenation of olefins.

- Polymerization of olefins through homogeneous catalysis.

Examples of exercises

-        -  Derive the number of active IR bands in a carbonyl compound.

-         - Derive the diagram of molecular orbitals of complexes with tetrahedral and octahedral geometry.