ADVANCED INORGANIC CHEMISTRY
To address successfully the topics of the course students must have solid knowledge in general and inorganic chemistry and in organic chemistry and chemical physics.
Course Objectives and expected learning outcomes
The course aims to illustrate the properties of coordination compounds. In particular, the focus will be on the nature of the different ligands, the coordination modes, the interaction metal/ligand, the coordination geometry, and on the main reactions at the metal center. After completing the course students, using the concepts learned, will also be introduced to the basic concepts of homogeneous catalysis.
At the end of the course students will be able to draw structure/reactivity correlations, gaining the ability to solve simple problems of coordination chemistry, e.g. how to predict molecular geometries, electronic structures or the reactivity of a particular species and they will also be able to understand (at least in outline) the scientific literature in the area of coordination chemistry.
Course Topics
1) Ligands (2 hours): Monodentate and polydentate ligands, Werner compounds
2) Structure, symmetry and stability of coordination compounds (6 hours):
Geometries and coordination numbers. Macrocycles, sepulcrants and sarcofagines. Template and macrocycle effects. Isomerism in coordination compounds. Optical isomerism. Stability of coordination compounds. Stability constants, stability correlations.
3) The bond in coordination compounds (10 hours): Crystal Field Theory. Splitting of d orbitals in an octahedral field. High and low spin, spin crossover. The spectrochemical series. Electronic spectra and magnetic properties of coordination compounds. Splitting in other geometries. Molecular orbital theory: sigma- and pi-interactions. Backdonation. The Angular Overlap Model. Coordination geometry/electron configuration relationships. Jahn-Teller distortion.
4) Organometallic compounds: synthesis and properties (15 hours): The 18 electrons rule. Formal oxidation states. Carbonyl complexes. Phosphine complexes. Molecular nitrogen and molecular oxygen as ligands. Oxo, superoxo and peroxo complexes. Molecular hydrogen and hydride complexes. Carbene complexes Olefin complexes. Complex containing cyclic polyenes.
5) Reactivity of coordination and organometallic compounds (15 hours):
Ligand substitution reactions in square planar and octahedral complexes.
Oxidative addition and reductive elimination. Insertion reactions. Electron transfer reactions. Introduction to homogeneous catalysis
Course Organization
The course will be taught through lectures in the classroom with the help of power-point projections.
Textbooks and other readings
The slides presented in class will be available to the student on the university e-learning platform in the days before the holding of the lesson. The following books are helpful for consultation:
1) D.F. Shriver, P.W. Atkins, Inorganic Chemistry, Oxford University Press
2) J. E. Huheey, E.A. Keitner, R. L. Keiter, Inorganic Chemistry, Harper Collins
3) F.A.Cotton, G. Wilkinson, C.A. Murillo, M. Bochmann, Advanced Inorganic Chemistry, John Wiley & Sons
Final Course Examinations
The assessment will be done through written and oral examinations. The written test will consist of three questions related to topics covered in the course (electronic counting, prediction of reaction products, interpretation of experimental data obtained from the literature). Passing the written test will allow the student to access the oral examination concerning concepts covered in the written text and in general in all the course. The final grade will be out of thirty.