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Hydride Elimination in Catalysis

Hydride elimination reactions involve the transfer of a hydrogen atom from a ligand to a metal. The most common type is β-elimination, where a proton in the β position of an alkyl ligand is transferred to the metal through a planar transition state. β-elimination is an important reaction in many catalytic processes. Abstraction reactions are another type of elimination reaction where a substituent is removed from a ligand by an external reagent like a Lewis acid, without changing the metal's coordination number.

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18 views4 pages

Hydride Elimination in Catalysis

Hydride elimination reactions involve the transfer of a hydrogen atom from a ligand to a metal. The most common type is β-elimination, where a proton in the β position of an alkyl ligand is transferred to the metal through a planar transition state. β-elimination is an important reaction in many catalytic processes. Abstraction reactions are another type of elimination reaction where a substituent is removed from a ligand by an external reagent like a Lewis acid, without changing the metal's coordination number.

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Nhu Tran
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14.2.

4 Hydride Elimination

Now, i will demonstrate you about the definition of Hydride elimination

First, Hydride elimination reactions are characterized by hydrogen atom


transfer from a ligand to a metal. The most common type of hydride
elimination is b-elimination, with a proton in a b position* on an alkyl
ligand transferred to the metal by way of an intermediate in which the
metal, the a and b carbons, and the hydride are coplanar.
I give you an example of b elimination—the reverse of 1,2-insertion—
is in Figure 14.15. Beta eliminations are important in many catalytic
processes.

Alkyl complexes without b hydrogens are more stable than those with
such hydrogens because only complexes with b hydrogens can undergo
these reactions (although the former may undergo other types of
reactions).
Furthermore, complexes containing b hydrogens that are coordinatively
saturated—that is, complexes in which all coordination sites are filled—
are more stable than complexes with empty coordination sites; the b-
elimination mechanism necessitates the transfer of a hydrogen to an
empty coordination site.
Other forms of elimination processes, such as the elimination of
hydrogen from the a and g locations, are also known.
Besides, i will give u one more example being alkoxide ligands bound to
late transition metal complexes

The mechanism shown indicates a four-center transition state in


which the hydride is transferred to the metal. In some cases, the
unsaturated fragment that is formed will remain bound to the metal
and in other cases it will either not bind or be displaced by a
stronger donor ligand.

An important prerequisite for b-hydride elimination is the presence


of an open coordination site on the metal complex. If no open site
is available, then it will be necessary to displace a ligand before the
reaction can occur. In addition, the metal complex will usually
have less than 18 electrons, otherwise a 20 electron olefin-hydride
would be the immediate product.

The microscopic reverse of a b-hydride elimination is called


an olefin insertion reaction. In many systems there is a rapid,
reversible equilibrium between the alkyl complex and the alkene-
hydride that results from b- elimination. b-elimination is a very
important chain termination step in the polymerization of olefins,
in the hydrozirconation reaction and in a variety of catalytic
processes.

So, In order to prevent b-elimination from taking place, one can


use alkyls that:
o Do not contain b-hydrogens.
o Are oriented so that the beta position can not access the metal
center.
o Would give an unstable alkene as the product.

Let move to a new part

14.2.5 Abstraction
About the definition Abstraction reactions

Abstraction reactions are elimination reactions in which the coordination


number of the metal does not change. In general, they involve removal
of a substituent from a ligand by the action of an external reagent, such
as a Lewis acid. Two types of abstractions, a and b, are illustrated in
Figure 14.16; they involve removal of substituents from the a and b
positions (with respect to the metal), respectively, of ligands. Alpha
abstraction is used to synthesize carbyne complexes.

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