Theoretical organometallic reactivity

Examples of homogeneous catalysis reactions will be presented, emphasizing the underlying concepts and limitations of theoretical approaches (mainly DFT). Olefin metathesis and examples of polymerization will illustrate supported catalysis, emphasizing 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

Targeted skills:

- establish links 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 terminal exam.

(1) Homogeneous catalysis

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

ML4 square plan, Walsh diagrams

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

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

(d) Redox chemistry: single- vs. two-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 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 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, volcano curves.

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

Administrative contact(s):

Master's Program in Chemistry Secretariat

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