Theoretical organometallic reactivity

Examples of homogeneous catalysis reactions will be presented, with emphasis on the underlying concepts and the limitations of theoretical approaches (mainly DFT). Olein metathesis and polymerization examples will illustrate supported catalysis, with emphasis on the influence of the support.

Various examples will illustrate the specificity of nanocatalysts, distinguishing the respective role of electronic and geometrical factors.

Hourly volumes* :

CM : 20

TD : 10

Targeted Skills:

- make the link between electronic properties, multi-step reaction mechanisms and experimental observations

- interpret the electronic structure of d- and f-metal complexes and organic and inorganic nano-objects

- identify the main methods used to explore chemical reactivity

Atomic and molecular orbitals; band structure of solids; ligand field theory; Hückel method

Written final exam.

(1) Homogeneous catalysis

(a) Ligand field, ligand classification, electron count, octahedral ML6 OM diagrams and

ML4 square plan, Walsh diagrams

(b) Atomic pseudopotentials, definition of chemical models, accuracy

(c) Some examples: bond activations (C-H, C-X), insertion, metathesis

(d) Redox chemistry: mono- vs. bi-electron transfer, activation of CO2, H2, N2

(e) Comparison between homogeneous and heterogeneous catalysis: Case of Ziegler-Natta polymerization

(2) Supported catalysis

(a) Some elements on the grafting surface (silica, alumina)

(b) Effect of surface area on a few selected reactions: Ring opening polymerization, polymerization of

olefins, olefin metathesis, bond activation

(3) Nanocatalysts

(a) Where are the electrons? Nature of the bonds ? Application to model systems (polymers and clusters)

organometallic).

(b) Size/morphology-catalytic activity relationship

(c) Fischer-Tropsch reaction, C-H activation, hydrogenation reactions

(d) Reactivity descriptors: BEP relation, Sabatier principle, volcano curves.

(e) Some of the major current issues: energy, biomass, CO2

Administrative contact(s):

Secretariat Master Chemistry

https://master-chimie.edu.umontpellier.fr/