Reactions of Organometallic Complexes

• Substitution

• Oxidative Addition

• Reductive Elimination

• Migratory Insertion

• β - Elimination

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 Reactions of Organometallic Complexes: Substitution

Ø Subs%tu%on: Subs%tu%on of ligand in complex with other ligand

M–L + L' M–L' + L

The subs%tu%on occurs provided the product also follows 18 e⁻ rule

Ø Examples:

Mo(CO) 6 + PPh 3 [Mo(CO) 5PPh 3] + CO

+
PPh 3 PPh 3
Ph 3P Rh Cl + Sol Ph 3P Rh Sol + Cl –
PPh 3 PPh 3

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 Oxidative Addition (OA)

• Increases formal oxida4on by two units

Coordinatively unsaturated Oxida%on (loss of two electrons)
complex in a relatively low
oxidation state • Increases its coordina4on number by two

• General representation:

[Y] Oxidation Addition

[Y+2]

• Example:

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 Oxidative Addition: Mechanism
Ø Oxida%ve Addi%on: Requirements
1. Availability of nonbonded electron density on the metal – low-valent metals. The
ease of oxidative addition: Co(I) < Rh(I) < Ir(I)
2. Two vacant coordination sites on the reacting metal complex (LnM). In other
words, requires coordinatively unsaturated metal centre
3. A metal with stable oxidation states separated by two units

Oxidative Addition is common for 16-electron square planar metal complexes

Ø Mechanism: Concerted Pathway – Non Polar X–Y with single bond (e.g. H2, aryl halide)

σ-complex transi%on state Cis product formed

[Three centre TS also proposed]
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 Oxidative Addition: Mechanism – Concerted Pathway

Ø Mechanism: Concerted Pathway – Non Polar X–Y with multiple bond (e.g. O2, CH2=CH2)

• The coordination of a olefin to a Example: Zeise’s salt

transition metal provides the simplest
example of a metal p-complex.

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 Oxidative Addition: Mechanism

Ø Mechanism: Concerted Pathway – Non Polar X–Y with mul%ple bond (e.g. O2, CH2=CH2)

π-complex transition state

Ø Mechanism: Non-Concerted Pathway – Polar X–Y

1. SN2 Mechanism (two electron transfer)

X and Y need not be cis

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 Oxidative Addition: Mechanism – Non-Concerted Pathway

Inversion at carbon has been found in subs%tuted halides

Reactivity of Metal
More nucleophilic the metal,
the greater its reactivity in SN2
additions

2. Radical Mechanism (one electron transfer) – Requires radical ini%ator

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 Reductive Elimination (RE)

Ø Reductive elimination is the reverse of Oxidative addition

• Decreases formal oxida4on by two units
Coordinatively saturated Reduc%on (gain of two electrons)
complex in a relatively high
oxidation state • Decreases its coordina4on number by two

• General representation:

Reduc%ve Elimina%on
[Y+2]

• Example:

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 Reductive Elimination (RE)

Ø Reduc%ve elimina%on is favoured for the complexes having:

1. Higher formal posi%ve charge on metal – electron poor (High oxida%on state
metal or poor donor ligands)
2. Presence of bulky group (ligand) on metal – Steric hinderance
3. cis-configura%on of the leaving groups
and the organic product formed should be stable.

Ø Reductive elimination efficient for: d6 –> PdIV, PtIV, RhIII, IrIII and d8 –> NiII, PdII, AuIII
Ø Mechanism is not well studied. Because, complexes that undergo RE are generally less stable.

Ø Concerted RE occurs with retention of configuration:

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 Migratory Insertion

Ø Migratory Inser%on: Reac%on of cisoidal anionic ligand (e.g. hydride or alkyl group) and
neutral ligand (e.g. CO) on the metal complex couple to generate a new coordinated
anionic ligand
vacant site

Ø General Features:
1. No change in the formal oxidation state of the metal
2. Two groups that react must be cisoidal to one another
3. A vacant coordination site is generated during a migratory insertion, which gets
occupied by the incoming ligand in order to stop the back elimination reaction.

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 Migratory Insertion

Ø Anionic and neutral ligands that can undergo migratory insertion with one another:
Anionic: H–, R– (alkyl), Ar– (aryl), acyl–, O2– (oxo)
Neutral: CO, Alkene, Alkynes, carbenes

Ø Type of Migratory Insertion:

Migrated group and metal are

separated by one atom
– Occurs in CO and carbenes (η1)

Migrated group and metal are

separated by two atom
– Occurs in alkenes and alkynes (η2)
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