Chemistry

Review of fundamental concepts (2 CFU) 1) Chemical kinetics. a) Definition of reaction rate. Kinetic laws and reaction order (first order, second order reactions. Definition of “steady state” and kinetic law. Kinetic law of pre-equilibrium reactions). b) Effect of temperature on the rate of a chemical reaction (Arrhenius' Law and Eyring's Activated Complex Theory). c) Some examples of kinetic equations. d) Catalysis and definition of catalyst. e) The Hammett equation and Linear Free Energy Relations. 2) Bonds in coordination compounds. a) Valence bond theory, principle of electroneutrality and backdonation. b) Crystal field theory (CFT) and the “spectrochemical series”; Octahedral, tetrahedral and square planar symmetry. c) Molecular orbital theory (Ligand field theory). Organometallic Chemistry (4 CFU) 1) Description of the main classes of organometallic complexes: structure and chemical-physical properties, 18 electron rule and stability. a) Metal - hydride complexes. b) Metal - carbonyl complexes. c) Metal - phosphine complexes. d) Metal complexes - unsaturated organic compounds and metallocenes. 2) Fundamental reactions and mechanisms of organometallic complexes. a) Ligand substitution reactions: associative, dissociative and exchange mechanisms; photochemical activation; electronic, structural and solvent effects. b) Oxidative addition and reductive elimination. c) Insertion (insertion) and reductive elimination reactions. 3) Introduction to homogeneous catalysis; Tolman cycles. a) Hydrogenation and hydroformylation of alkenes. b) Polymerizations of alkenes; Ziegler-Natta stereospecific polymerization of propene. c) The Monsanto methanol carbonylation process.

Knowledge of the fundamental aspects of inorganic chemistry and physical chemistry. Knowledge of the basic concepts of kinetic theory and fundamental reaction mechanisms.

Texts on the fundamentals of chemical kinetics and reaction mechanisms 1) H. Maskill. The Physical Basis of Organic Chemistry. Oxford Science Publications. 2) R.A.Y. Jones. Physical and Mechanistic Organic Chemistry. Cambridge University Press. Texts on the fundamentals of coordination chemistry J.E. Huheey, E.A. Keiter, R.L. Keiter. Inorganic Chemistry, Principles of structure and reactivity. Harper-Collins College Publ. Texts on the reactivity of inorganic and organometallic complexes 1) J.D. Atwood. Inorganic and Organometallic Reaction Mechanisms. Wiley-Interscience Publ. 2) R.H. Crabtree. The Organometallic Chemistry of the Transition Metals. Wiley-Interscience Publ.

La frequenza del corso è libera e non prevede test intermedi o esercitazioni di laboratorio.

The evaluation of the knowledge acquired is based on an oral interview, possibly concerning a topic chosen by the student among those illustrated during the course. Subsequent questions will accompany the test to evaluate the general preparation of the students.

The course includes lectures on the topics indicated in the program.