Organometallic Compounds in Catalysis



Introduction
Hydrogenation of Alkenes
Hydroformylation of Alkenes



Introduction

The International Union of Pure and Applied Chemistry defines catalysis as the phenomenon in which a relatively small amount of a foreign material, called a catalyst, augments the rate of a chemical reaction without itself being consumed. In practice this means that a catalyst reduces the activation energy of a reaction, which must itself be energetically favoured.


Organometallic compounds are important in many catalytic reactions involving organic molecules. Catalytic activity occures widely among the transition metals, but there are also a few instances where main group compounds act as catalysts. In many cases a series of steps can be drawn up in which transition metal complexes undergo a sequence of oxidative addition, insertion and reductive-elimination reactions. During the sequence the organic reactants are converted into the product and the transition metal complex is regenerated so that the sequence forms a closed loop called a "catalytic cycle". Catalytical cycles can be studied by: Spectroscopy (NMR, IR), Isotopic labelling, Optical activity (reflects stereochemical changes during a reaction).

Note:

  1. "Catalyst" added to the reaction may not be the "Active catalyst".
  2. Intermediates isolated from the reaction may be products of side reactions - BE CAUTIOUS !!!
  3. True catalysts are very reactive and are, therefore, not easily isolable.

(Reference 3)


Catalysts can be heterogeneous (in different phase eg: gases passing over a metal surface) or homogeneous.
Homogeneous catalysis: that means the catalysis is in the same phase as the reactants and the products, for organometallic compounds, this is usually means in solution.

Advantages      - all atoms present are potential catalytic centres.
                        - a homogeneous catalyst gives reproducible results because it has a definite stichiometry and structure.
                        - specificity of the catalyst can be modified.

Disadvantages  - can be difficult to seperate catalyst from products.
                        - increasing the rate through heating may couse problems with the stability of the organometallic catalyst.


What makes a good catalyst?

  1. The ability to alter its coordination number, that means to undergo additions & eliminations.
  2. Variable oxidation states - 2 stable states at least 2 units apart.
  3. The property of bringing 2 molecules together - enhancing their reactivity.
  4. Selectivity with respect to ligands - accepts desired ligands
                                                       - rejects alternative, but non-reactive ligands.
    (CO, PR3, SR2 can act as 'poisons', because of the strong bonds they form with metals.)