Informations

Langue d'enseignement : Français
Crédits ECTS: 6

Programme

• Heures d'enseignement dispensées à l'étudiant : 51 heures
• Temps de travail personnel : 125 heures

Objectifs et compétences

Objectifs :
The objective of this lecture is, via the study of the chemical bonding, to allow the student to connect structure / composition and reactivity / properties of compounds, and this for organic molecules, transition metal complexes or solid state compounds. Special attention will be paid on the introduction to the frontier orbital approximation and its use to address the problems of absolute and relative reactivity, regioselectivity and stereoselectivity in organic chemistry (Woodward-Hoffman rules, electrocyclic reactions, sigmatropic rearrangements,…); properties of transition metal complexes (Tanabe-Sugano diagrams, Marcus law, Curie law) and chemical bond in solids (ionic models, band theory (orbital description of the electronic structure of solids),…).

Recommanded prerequisites:

FRONTIER ORBITALS AND ORGANIC CHEMICAL RECATIONS

Molecular orbitals and their representation as linear combination of atomic orbitals. Basics on Hückel molecular orbital theory. Basics in organic chemical reactions (nucleophilic or electrophilic addition and substitution, rearrangements, cycloadditions, etc…).

MOLECULAR INORGANIC CHEMISTRY.

Symmetry and shape of d orbitals, basis of crystal field theory (octahedral symmetry), notion of redox potential, elementary notions of thermodynamics (K, DG, DH, DS), elements of kinetic (first and second order kinetic), elementary notions on molecular orbitals applied to transition metal complexes.

CHEMICAL BONDS IN SOLIDS

Stacking and crystal structure of simple metallic or ionic coumpounds. Covalent bond model for a molecule (Hückel, LCAO). Shape and symmetry of d orbitals, crystal field theory (octahedral symmetry). Electronegativity.

Lesson program:

FRONTIER ORBITALS AND ORGANIC CHEMICAL RECATIONS

1- Fundamental in quantum chemistry: molecular orbitals of conjugated polyene systems (Hückel theory), frontier orbitals approximation

2- Cycloaddition reactions: Woodward-Hoffmann rules, activation mode and reactivity, interactions suprafacial and antarafacial interactions, regioselectivity and stereoselectivity (Alder endo rule).

3- Electrocyclic reactions: selection rules and activation mode, conrotatory and disrotatory ring closing/opening, stereoselectivity aspects

4- Sigmatropic rearrangements: selection rules (suprafacial and antarafacial), stereoselectivity aspects.

5- Electrophilic, nucleophilic and radical reactions

6- Structural problems: stable conformation, hyperconjugation

MOLECULAR INORGANIC CHEMISTRY

1- Electronic structure of complexes. General information on d elements. d orbitals. Crystal field theory. Tanabe-Sugano diagrams. Charge transfer transitions. Application: spin crossover phenomena.

2- Stability and reactivity of complexes. Stability of a complex: thermodynamic and kinetic aspects.

Modification of chemical properties of the metal and the ligand in a complex. Electron transfer. Marcus law.

3- From molecules to molecular materials. Synthesis of polynuclear compounds. Molecular magnetism. Illustration with mono- and dinuclear compounds.

CHEMICAL BOND IN SOLIDS

1- Introduction: classification for solids; electrons in solids

2- Ionic model: crystal energy, Madelung potentials, energy levels (Koopmans theorem), structure of ionic solids (Pauling rules, Brown method)

3- Chemical bond and energy levels in simple metals and transition metals

4- Band theory: orbital description if the electronic structure in solids.

Electronic structure of 1D compounds, dimers and n-mers formation (Peirls distorsion), Electronic structure of 2D and 3D compounds.

Examples of transition metal oxides: electronic structure and electric properties.

Organisation pédagogique

le mode de fonctionnement de l'UE est présenté au début des enseignements

Contrôle des connaissances

Assessment methods and criteria

1st session

Written examination (3h00) - coef. 1.0.

To obtain a mark over 7/20 is mandatory for Master 1 diploma

2nd session

Written or oral examination (depending on the students number, if written exam: 3h00) - coef 1.0

Lectures recommandées

l'ensemble des références bibliographiques est communiqué au début des enseignements

Responsable de l'unité d'enseignement

- Non défini -

Enseignants

la composition de l'ensemble de l'équipe pédagogique est communiquée au début des enseignements