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Organometallic Reaction

The document summarizes various types of organometallic reactions involving modification of ligands. It describes insertion reactions where a molecule inserts into a metal-ligand bond, including 1,1 and 1,2 insertions of molecules like CO and olefins. It also discusses carbonyl insertion and alkyl migration mechanisms. Hydride elimination reactions are described where an alkyl ligand undergoes beta elimination. Finally, abstraction reactions are mentioned which eliminate ligands without changing the metal's coordination number.

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Fikri Zacky Aditama
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191 views22 pages

Organometallic Reaction

The document summarizes various types of organometallic reactions involving modification of ligands. It describes insertion reactions where a molecule inserts into a metal-ligand bond, including 1,1 and 1,2 insertions of molecules like CO and olefins. It also discusses carbonyl insertion and alkyl migration mechanisms. Hydride elimination reactions are described where an alkyl ligand undergoes beta elimination. Finally, abstraction reactions are mentioned which eliminate ligands without changing the metal's coordination number.

Uploaded by

Fikri Zacky Aditama
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PPTX, PDF, TXT or read online on Scribd
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Organometallic

Reaction
By:
Dwi Susanti 1403705
Fathyyah Zulfa 1406559
Fikri Zaki Aditama 1406385
Outlines

Reactions involving modification of ligands


1. Insertion
2. Carbonyl insertion (alkyl migration)
3. Hydride elimination
Abstraction
REACTIONS INVOLVING MODIFICATION OF LIGANDS

1. Ligand Dissociation and Substitution


- Insertion reactions

Insertion reaction is a reaction in which a molecule/


molecular parts to put himself into the bond between
the two parts of chemical molecules that enter or insert
a molecule into the molecular bonds of the latter.

This reaction does not cause a change in the oxidation


state of the metal center.
1,1 insertion
In a 1,1-insertion, metal and X group "move" to the same atom
of the inserting substrate.
The metal-bound substrate atom increases its valence
CO, isonitriles (RNC) and SO2 often undergo 1,1-insertion
Insertion of CO and isonitriles
CO insertion is hardly exothermic.

An additional ligand may be needed to trap the acyl


and so drive the reaction to completion.

In the absence of added ligands often fast equilibrium.

CO insertion in M-H, M-CF3, M-COR endothermic.


no CO polymerization.
but isonitriles do polymerize!
1,2 insertion
1,2 insertions give products in which bonds to the
inserted molecule are made to adjacent atoms in that
molecule
Examples:
Application of 1,2 insertions
Insertion of an olefin in a metal-alkyl bond produces a
new alkyl
Thus, the reaction leads to oligomers or polymers of the
olefin.
One such process is the Cossee-Arlman mechanism,13
proposed for the Ziegler-Natta polymerization of alkenes
According to this mechanism, a polymer chain can grow
as a consequence of repeated 1,2 insertions into a
vacant coordination site, as follows:
Mechanism of olefin insertion
Standard Cossee mechanism
R
M M M M
R R R

Green-Rooney variation (a-agostic assistance):


CH2P
M M M M
CH2P CH2P
H H
P
Interaction with an a C-H bond could facilitate tilting of the migrating alkyl group
The "fixed" orientation suggested by this picture is probably incorrect
1,2-insertion of olefins

the reaction leads to oligomers or polymers of the olefin.


Best known polyolefins:
polyethene (polythene)
polypropene
In addition, there are many specialty polyolefins.

Polyolefins are among the largest-scale chemical products


made.
They are chemically inert.
Their properties can be tuned by the choice
of catalyst and comonomer.
2. Carbonyl Insertion (Alkyl Migration)

Migration vs. Insertion


A migration is when the anionic ligand moves
and performs a nucleophillic-like intramolecular
attack on the electrophillic neutral ligand
An insertion is when the neutral ligand moves
and inserts into the bond between the metal
and anionic ligand
The anionic ligand can be: H (hydride),
R (alkyl), acyl, Ar (aryl), or OR (alkoxide)
The neutral ligand can be: CO, alkene, alkyne, or in
some cases, even carbene
Carbonyl Insertion (Alkyl
Migration)
The insertion of CO into a M-C bond in alkyl complexes
is of particular interest in its potential applications to
organic synthesis & catalysis

3 plausible mechanisms have been suggested for the


reaction :
Mechanism 1 : CO insertion
Mechanism 2 : CO migration
Mechanism 3 : Alkyl migration
Mechanism 1: CO insertion

Direct insertion of CO into metal-carbon bond


Mechanism 2: CO migration

Migration of CO to give intramolecular CO insertion. This


would yield a 5-coordinate intermediate, with a vacant site
available for attachment of an incoming CO
Mechanism 3: Alkyl migration
In this case, the alkyl group would migrate, rather than the
CO, & attach itself to a CO cis to the alkyl. This would also
give a 5-coordinate intermediate with a vacant site
available for an incoming CO
3. Hydride Elimination

Hydride elimination (usually by b hydrogens)


Many transition metal alkyls are unstable (the reverse of
insertion)
the metal carbon bond is weak compared to a metal hydrogen
Bond Alkyl groups with hydrogen tend to undergo elimination

M -CH -CH3 M - H + CH2=CH2


Two examples2
A four-center transition state in which the hydride is transferred to the metal
An important prerequisite for beta-hydride elimination is the presence of an open
coordination site on the metal complex - no open site is available - displace a ligand
metal complex will usually have less than 18 electrons, otherwise a 20 electron
olefin-hydride would be the immediate product.

To prevent beta-elimination from taking place, one can use alkyls that:
Do not contain beta-hydrogens
Are oriented so that the beta position can not access the metal center
Would give an unstable alkene as the product
Other -Elimination Reactions
Applications of -Eliminations

The inorganic perspective, which focuses on the metal


center
recognize that -hydride elimination has the wonderful side
effect of establishing an MH bonda feat generally difficult to
achieve in a selective manner via oxidative addition of XH.
The organic perspective, which focuses on the ligands
the organic ligand is oxidized in the course of -hydride
elimination.
Abstraction Reaction
Abstraction reaction is an elimination reaction of ligands that will not change the
metal coordination number.

Examples of this
reaction is:
In the above reaction (in the box) called abstraction
reaction occurs due to the disposal of substituent i H atoms
in the ligand-exo-RC5H5 4-5 (tetrahapto) caused by
reagents Ph3CPF6. H atoms from the exhaust, then ligand-
exo-RC5H5 4-5 turned into 5-RC5H4. The coordination
number of metal in this reaction does not change, but
change the oxidation state of the metal Fe Fe (0) to Fe (II).
Thank You

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