Theoretical organometallic reactivity

Examples of homogeneous catalysis reactions will be presented, highlighting the underlying concepts and 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 between the respective roles of electronic and geometric factors.

Hourly volumes* :

CM: 20

TD : 10

Target skills :

- link 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, precision

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

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

(e) Comparison of homogeneous and heterogeneous catalysis: the case of Ziegler-Natta polymerization

(2) Supported catalysis

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

(b) Effect of surface on selected reactions: Ring-opening polymerization, polymerization of

olefins, olefin metathesis, bond activation

(3) Nanocatalysts

(a) Where are the electrons? Nature of 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 relationship, Sabatier principle, volcano curves.

(e) Some of today's major challenges: energy, biomass, CO2

Administrative contact(s) :

Secretariat Master Chemistry

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