ORGANOMETALLIC CHEMISTRY
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- Versione italiana
- Academic year
- 2017/2018
- Teacher
- ELEONORA POLO
- Credits
- 6
- Didactic period
- Primo Periodo Didattico
- SSD
- CHIM/03
Training objectives
- The course gives a thorough introduction to metallorganic chemistry and the tools to study metal-carbon bonds, thus integrating and expanding the knowledge acquired in Organic and Inorganic Chemistry courses. The course deals with the synthesis, characterization techniques and reactivity of metallorganic compounds of both Group A and transition metals, their use as reagents and/or catalysts in laboratory and some important industrial processes.
After completion of the full course the student should have gained knowledge about:
•Types of bond, structure and stereochemistry of the compounds of transition metals, and of the principal series.
•Stability and reactivity of metallorganic complexes.
•Mechanism of the main organometallic reactions and of some catalytic processes commonly used in organic synthesis and in industrial processes.
•Analytical techniques required to characterize metallorganic complexes and reaction intermediates.
The basic acquired abilities (that is, the capacity of applying the acquired knowledge) will be:
•Recognize and classify (electron counting, oxidation state, coordination number) metallorganic complexes.
•Understand and foresee the reactivity of a compound on the basis of the M-C bond types and of the valence electrons of the metal.
•Plan the synthesis of simple metallorganic compounds.
•Know how to use metallorganic compounds as reagents/catalysts in organic syntheses and in some industrial processes. Prerequisites
- Although the Prospectus does non require preparatory courses, in order to fruitfully follow the lectures, the student should have knowledge of the fundamental concepts of inorganic, organic, and coordination chemistry.
Course programme
- The course takes 36 hours of frontal lectures.
Introduction (8 hours)
Definition of metallorganic compound, energy, polarity and reactivity of the M-C bond. Electron counting methods and 18 electrons rule, their application and limits.
Metallorganic compounds of transition metals: type of reactions (8 hours)
Organometallic reaction mechanisms thoroughly discussed: ligand substitution, isomerisation, hapticity change, transmetallation, oxidative addition, reductive elimination, migratory insertion, elimination, nucleophilic, and electrophilic addition at ligands and metals.
Metallorganic compounds of transition metals: mechanism for some commonly used industrial and laboratory catalytic processes(5 hours)
The accumulated know-how serves as the foundation for discussions about how organometallic complexes are utilized in catalysis (i.e., Cross-coupling reactions, hydrozirconation, hydrogenation, metathesis), and in selected important industrial processes (hydroformilation, polymerisation CO/alkenes, Ziegler-Natta type polymerisation, ADMET and ROMP).
Metallorganic compounds of s and p groups (5 hours)
Definition, structure, stability, synthesis, reactivity, and applications.
Metallorganic compounds of transition metals: families of metallorganic compounds according to the ligands (6 hours)
General properties, syntheses, and reactions of several metallorganic compounds classified according to their ligands are described. Different reactive ligand types are discussed, including sigma-bonded ligands (alkyl, aryl, hydride; oxygen-, nitrogen- and phosphorus- based ligands) as well as pi-bonded ligands such as phosphines, carbonyls, alkenes, dienes, cyclopentadienyls, carbenes, and arenes.
Characterisation (4 hours)
Relevant analytical techiniques for the characterization of metallorganic compounds, and reaction intermediates (NMR, IR, ESR, UV/Vis, X-ray diffraction, MS, …). Didactic methods
- The course is organized as frontal lectures on all the course’s topics, and includes also exercises on electron counting.
Learning assessment procedures
- The aim of the exam is to verify at which level the learning objectives previously described have been acquired.
The oral exam will investigate the knowledge in four different areas:
•Determination of the oxidation state, coordination number and electron counting of a given compound using all the methods studied (ionic, covalent, and CBC)
•Individuation of the most appropriate analytical techniques required for a full characterisation of the above compound
•Description of the mechanism of one of the organometallic reaction types and/or a catalytic process
•Description, synthesis, and reactivity of a particular class of metallorganic compounds
To pass the exam it is necessary to get at least 18 points out of 30. Reference texts
- All the material presented will be available to students.
Textbooks that the students may already own from previous courses. They contain the background materials:
D. Shriver, P. Atkins, "Inorganic Chemistry", Oxford University Press; 5th Ed (2009)
J. Clayden, N. Greeves, S. Warren, P. Wothers, "Organic Chemistry", OUP Oxford, 2001
Metallorganic chemistry textbooks (a copy of each one is available and can be borrowed at the University chemical-biological Library S.Maria delle Grazie).
•D. Astruc "Organometallic Chemistry and Catalysis", Springer, Berlin, 2007
•C. Elschenbroich "Organometallics", 3rd Ed., Wiley-VCH, New York, 2007
•R.H. Crabtree "The Organometallic Chemistry of the Transition Metals", 5th Ed., Wiley-VCH, New York 2009
•A.F. Hill "Organotransition Metal Chemistry", The Royal Society of Chemistry, Cambridge (UK), 2002
