Hydride Elimination

INORGANIC
CHEMISTRY 4
SRIATUN, S.SI, M.SI

DEPT. OF CHEMISTRY FSM
DIPONEGORO UNIVERSITY
REACTION INVOLVING MODIFICATION LIGANDS
 HYDRIDE ELIMINATION
 ABSTRACTION
 SRIATUN, S.Si, M.Si

 DEPT. OF CHEMISTRY FSM
 DIPONEGORO UNIVERSITY
HYDRIDE ELIMINATION
Hydride elimination reactions are characterized by hydrogen

atom transfer from a ligand to a metal. The type of hydride
elimination:
• β- elimination: in β position on an alkyl ligand transferred to
the metal by way of an intermediate in which the metal, the
α and β carbons, and the hydride are coplanar.
• Example: 1,2 insertion is reverse of β- elimination
• β eliminations are important in many catalytic processes.
Because only complexes that have β hydrogens can undergo
these reactions, alkyl complexes that lack β hydrogens tend to
be more stable than those that have such hydrogens.
• Furthermore, coordinatively saturated complexes—
complexes in which all coordination sites are filled—
containing β hydrogens are in general more stable than
complexes having empty coordination sites;
• the β elimination mechanism requires transfer of a hydrogen
to an empty coordination site.
• Finally, other types of elimination reactions are also known,
such as the elimination of hydrogen from α and ϒ position.
ABSTRACTION
• Abstraction reactions are elimination reactions in which the

coordination number of the metal does not change.
• 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, α and β removal of substituents

from the α and β position.
NUCLEOPHILIC ADDITION TO THE LIGAND
A nucleophile may attack an organometallic complex—substituted with at least one

unsaturated ligand (e.g., CO, alkene, polyene, arene).
Reactions of Nucleophiles
with Metal Complexes
a: involves nucleophilic attack at the
metal, importance with regard to
transmetallation reactions in which alkyl,
alkenyl, alkynyl, and aryl groups may be
transferred from either ionically bonded
main group organometallic compounds,
such as Grignard reagents, or more
covalent compounds, such as R-Hg-Cl.
b: involves nucleophilic attack at the

metal, but instead of displacement, a syn
insertion of an unsaturated ligand between
the metal and the nucleophilic ligand can
occur.
c: the nucleophile attacking the ligand. It is this route that we shall

consider in our discussion of nucleophilic reactions, because such
a pathway offers the chemist numerous possibilities for
accomplishing synthetic transformations that would be impossible
without the presence of the metal. The hapticity of the p ligand
decreases by one and the overall charge on the complex becomes
more negative by one unit.
The tendency for a nucleophile to attack an unsaturated ligand
directly is a function of the electron density on the metal (i.e.,
complexes with a formal positive charge on the metal are more
reactive than neutral ones), the degree of coordinative saturation
of the metal (unsaturated metals have a higher probability of
attack directly at the metal), and the presence of p-electron
attracting ligands (such as CO) that can absorb some of the
increased electron density on the metal after attack has
occurred.
NUCLEOPHILIC ABSTRACTION
The possibility exists for a nucleophile to attack the

ligand in such a way that part or all of the original ligand NUCLEOPHILIC ABSTRACTION
is removed along with the nucleophile.
Abstraction of alkyl groups by nucleophiles is relatively

uncommon, because reduced metals are generally poor
leaving groups.
• If the metal fragment is first oxidized, however,
nucleophilic attack on alkyl ligands at the carbon
attached to the metal becomes much more feasible.
• Oxidation makes the leaving metal fragment less basic
and also weakens the M-C bond.
• Br2 and I2 serve effectively as M-C cleaving agents.
Pathways for Oxidatively-Driven Nucleophilic Abstraction
Acyl group
nucleophile
Nucleophilic Abstraction
of σ-acyl Pd Complexes
Palladium is the metal readily forms σ–M-C

complexes, which then undergo facile CO insertion
and subsequent σ–acyl-Pd bond cleavage with a
variety of nucleophiles.

Hydride Elimination

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INORGANIC

SRIATUN, S.SI, M.SI

 SRIATUN, S.Si, M.Si

Hydride elimination reactions are characterized by hydrogen

• Abstraction reactions are elimination reactions in which the

Two types of abstractions, α and β removal of substituents

A nucleophile may attack an organometallic complex—substituted with at least one

b: involves nucleophilic attack at the

c: the nucleophile attacking the ligand. It is this route that we shall

The possibility exists for a nucleophile to attack the

Abstraction of alkyl groups by nucleophiles is relatively

Palladium is the metal readily forms σ–M-C

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