Learning objectives
At the end of the course the student is able to know, understand and apply the essential concepts of the chemistry of coordination compounds, in particular as regards the metals of block d. The student will show: a good knowledge of the most common coordination numbers and associated geometries, understanding of the quantum mechanical basis for describing complexes, understanding the thermodynamic and kinetic basis of the chemistry of complexes.
The student will develop those communication skills, that ability to learn and make connections between the various topics, and which will allow to deal with the scientific literature about coordination chemistry, even in its various application aspects.
Prerequisites
Basic knowledge of inorganic and organic chemistry
Course unit content
Introduction to the chemistry of coordination compounds (metal complexes). Werner's theory (primary and secondary valence). Nomenclature of coordination compounds. Ligands (denticity, coordination modes, cyclic ligands). Coordination number, coordination geometry. Isomerism and chirality in complexes. Hard and soft acids and bases (HSAB) theory.
The bond in the coordination compounds: outline of crystal field theory. Introduction to the theory of molecular orbitals (covalent model). Electronic and magnetic properties of the complexes. Jahn-Teller effect.
Thermodynamic aspects of the chemistry of coordination compounds. Selectivity of a ligand for a metal ion. Ionophores. Kinetic aspects of the chemistry of coordination compounds, substitution reactions and trans effect. Redox reactions. Template reactions.
Some examples of applications of coordination chemistry, in particular in bioinorganic chemistry.
Full programme
Introduction to the chemistry of coordination compounds (complexes). Werner's theory (primary and secondary valence). Nomenclature of coordination compounds. Ligands (denticity, coordination modes, cyclic ligands). Coordination number, coordination sphere, coordination geometry. Isomerism and chirality in complexes. Hard and soft acids and bases (HSAB) theory. Bond in the coordination compounds: outline of crystal field theory (energy separation of d orbitals, octahedral, tetrahedral and square planar fields). Stabilization energy of the crystal field. Strong and weak fields, spectrochemical series, low and high spin complexes. Outline of the theory of molecular orbitals (covalent model). Electronic and magnetic properties of the complexes. Jahn-Teller effect. Thermodynamic aspects of the chemistry of coordination compounds (formation constants, chelating effect, macrocyclic effect, Irving-Williams series). Selectivity of a ligand for a metal ion. Ionophores. Kinetic aspects of the chemistry of coordination compounds, substitution reactions and trans effect. Redox reactions (internal sphere mechanism, external sphere mechanism).
Coordination chemistry and bioinorganic chemistry: chelation therapy; inhibition of the activity of a metalloenzyme; metal complexes as drugs or supplements; metal complexes in radiodiagnostics and radiotherapy.
General characteristics of the coordination chemistry of lanthanides. “Antenna” effect. Metal complexes in Nuclear Magnetic Resonance imaging. Fluorescent probes (molecular probes).
Bibliography
Before the start of the course, the slides used for lessons will be available online.
J.R. Gispert, Coordination Chemistry, Wiley
J.E. Huheey, E.A. Keiter, R.L. Keiter, Chimica Inorganica. Principi, strutture, reattività, Piccin
D.F. Shriver, P.W. Atkins, C.H. Langford, Chimica Inorganica, Zanichelli
F. Basolo, R. Johnson, Chimica dei composti di coordinazione, Zanichelli
Teaching methods
The course will be carried out through lectures accompanied by
projection of slides; these will be
available online from the beginning of the course. The slides are an integral part of the teaching material.
Attention will be paid to use examples taken from “everyday life”, to underline links between the various parts of the course, to encourage students' active participation.
Assessment methods and criteria
The achievement of knowledge and understanding of the contents of the course will be ascertained through an oral test.
If the health emergency makes it necessary, the exam will still be oral, but in remote mode.
Other information
The slides of the course are available.
It is possible, by appointment, to arrange a meeting or a video call with the teacher.
