Theoretical Organometallic Reactivity

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

Various examples will illustrate the unique characteristics of nanocatalysts, distinguishing between the respective roles of electronic and geometric factors.

Hourly volumes*:

CM: 20

TD: 10

Target Skills:

- establish a connection between electronic properties, multistep reaction mechanisms, and experimental observations

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

- Identify the main methods used to study chemical reactivity

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

Final written exam.

(1) Homogeneous catalysis

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

ML4 square-plane, Walsh diagrams

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

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

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

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

(2) Supported catalyst

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

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

olefins, olefin metathesis, bond activation

(3) Nanocatalysts

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

(organometallic compounds).

(b) Relationship between size/morphology and catalytic activity

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

(d) Reactivity descriptors: BEP relationship, Sabatier principle, volcanic curves.

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

Administrative contact(s):

Master's in Chemistry Office

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