Oxidative addition is a fundamental organometallic reaction where a transition

metal complex adds a molecule, increasing the metal's oxidation state and
coordination number. In other words, the metal becomes oxidized by two
electrons as the coordination number increases by 2 ligands. This
reaction is crucial and often the first step in many catalytic cycles.

Factors Fascilitating oxidative addition reaction

 Metals should have low oxidation

 Metals should be coordinatively unsaturated i.e requires a vacant
coordination site for this reason OA are common for four or five
coordination complex.
 Non bonding electron density on the metal
 Metal should have stable oxidation state separated by two units
 Oxidative addition can occur in square planar TM complexes with d 8/
d10 configuration.

Oxidative addition of Ir(I) to Ir(III) is common while Oxidative addition of Fe(IIII)

to Fe(V) is possible but unlikely to occur.

Key Characteristics:
 Increased Oxidation State:The metal's oxidation state increases by two units upon
addition of the molecule.
 Increased Coordination Number:The coordination number of the metal also
increases by two, as two new ligands are added to the metal center.
 Cis or Trans Addition:The two added ligands can be either cis or trans to each other
in the resulting complex.
 Two new anionic ligands are added to the metal

Three major types of groups adds in an Oxidative addition reaction

 Non polar/low polarity compounds(H2, H-SiR, R-H, Ar-H,R-SH, X2 )

 Polar compounds (HX, RX, Ar-x,RCoX)

 Ligands with π systems (O2, alkenes, alkynes)
Depending on the nature of adding groups Oxidative addition product can
occur in a cis- or trans-fashion. Non polar groups usually adds in the cis
fassion while polar groups adds in the trans or cis fassion.

A classic example is the oxidative addition of H2 to Vaska's complex (trans-

[Ir(PPh3)2(CO)Cl]), forming an octahedral complex with two hydride ligands and two
phosphine ligands in cis positions.

When ligands with pi systems adds, a mettalacycle is formed where

the ligand remains [Link] ligands are called intact ligands. In
these cases the bond order between two atoms in the ligand is
decreased, but the bond order is still at least 1. For example, the
alkyne ligand shown below decreases from a carbon-carbon bond order
of three to a bond order of two after it binds to Pt.

Representation of all forms of addition

 Mechanisms of Oxidative additions

Oxidative Addition

Oxidative additions proceed by 3 Main Mechanisms depending on the metal center

and the substrates.

Concerted pathway

Oxidative additions of nonpolar substrates such as hydrogen and hydrocarbons appear

to proceed via concerted concerted pathways. Such substrates lack π-bonds,
consequently a three-centered σ complex is invoked, followed by intramolecular
ligand bond cleavage of the ligand (probably by donation of electron pair into the
sigma* orbital of the inter ligand bond) to form the oxidized complex. The resulting
ligands will be mutually cis,[2] although subsequent isomerization may occur.
Non-concerted Oxidative Addition Mechanism
Non-concerted oxidative addition mechanism is like nucleophilic
displacement (SN2) reaction. Usually, Polarized substrates, such as methyl,
allyl, and benzyl halides, undergo non-concerted oxidative addition
mechanism.

This mechanism is often assumed in the addition of polar and electrophilic

substrates, such as alkyl halides and halogens.

Radical Mechanism
 Alkyl halides can react with the metal center of a complex through
radical reaction.
 Other byproducts can form through the radical reaction.
 Radical reactions are sensitive to dioxygen due to it’s a paramagnetic
property.
 There are two types of radical mechanism: Non-chain and Chain radical
mechanism.

Oxidative addition and reductive elimination are invoked in many catalytic

processes in homogeneous catalysis, homogeneous catalysis,
e.g., hydrogenations, hydroformylations, hydrosilylations, etc.[5] Cross-coupling
reactions like the Suzuki coupling, Negishi coupling, and the Sonogashira
coupling also proceed by oxidative addition

Reductive Elimination Reactions

Reductive Elimination is the opposite of the oxidative addition where the
oxidation state of the metal center of the complex decrease by two units.
Unlike oxidative addition, reduction elimination only has one mechanism
which is the counter part of the concerted oxidative addition mechanism.

Reductive elimination,is most often seen in higher oxidation states because the formal oxidation
state of the metal is reduced by two units in the reaction
Features

 Ligands must be in a cis position in order to undergo reductive

elimination.
 is most often seen in higher oxidation state metals
 The eliminating ligands are always X-type
 Each anionic ligand will donate one electron to the metal
reducing the oxidation state of the metal by two units
 Reductive elimination is an intramolecular reaction and favored by low
electron density of the metal center.
 Coordination number of metal will decrese by two units.
 On the whole, the oxidation state of the metal decreases by two
units, two new open coordination sites become available, and an
X–Y bond forms.
 The reaction is especially efficient for intermediate oxidation states, such as the d8 metals
Ni(II), Pd(II), and Au(III) the d6 metals Pt(IV), Pd(IV), Ir(III), and Rh(III)

The cis-orientation of the two hydrido ligands is necessary to form an

H-H bond on elimination.
Factors fascilitating reductive elimination reaction

A high formal positive charge on metal

The presence of bulky groups on the metals

An electronically stable organic product.

A Reductive elimination can be stimulated by oxidation or photolysis.

Certain groups are more easily eliminated than others. The following reactions often proceed to the
right for thermodynamic reasons:

Reactions that involve H are particularly fast (the first 3 above) .

In catalysis reactions, a reductive elimination is often the last step in a catalytic cycle, and the
resulting LnM fragment must be able to survive long enough to react with the substrates for the
organic reaction and so reenter the catalytic cycle.
Octahedral d6complexes of Pt(IV), Pd(IV), Ir(III), and Rh(III) tend to undergo reductive
elimination readily but often with initial loss of a ligand to generate a 5-coordinate intermediate,
a much more reactive species than the starting 6-coordinate complex. When ligand dissociation
does not occur, reductive elimination can be slow, even when it would otherwise be expected to
be very favorable.
Other examples

MIGRATORY INSERTION (MI) REACTION Check pg 186 of TM complete note

This is the insertion of an unsaturated ligand eg CO, C2H4 between two other groups(atoms)
initially bonded together. In a migratory insertion reaction, an anionic
ligand (X−) and a neutral unsaturated ligand (L) couple to form a new
anionic ligand (−LX)that is attached to the same metal. The overall
result is that an M-X bond is broken and M and X are added across
a π bond of L. There is no change in oxidation state at the metal
(unless the ligand is an alkylidene/alkylidyne), but the total electron
count of the complex decreases by two during the actual insertion
event.

Features of Migratory insertion reaction

 The formal oxidation state does not change during the reaction.
 M I creates a vacant site which is being occupied by the incoming ligands
  Conversely,the elimination requires a vacant site, so that an18e complex will not undergo
the reaction unless a ligand first dissociates.
 The two ligands undergoing MI must be cis to one another
 Two ligands which are trans to one another never undergo MI
 MI is favoured on more electron deficient metals.
 If migratory ligand is chiral,then the reaction usually proceeds with retention of
configuration at chiral carbon.
 If there are two different alkyl groups coordinated to the metal, then the alkyl group
which is more electron rich will be a better nucleophile for migration.
 t-but > i-prop > et >me>phCH2
There are two main types of insertion
1) 1,1 insertion in which the metal and the X ligand end up bound to the same (1,1) atom

2) 1,2 insertionin which the metal and the X ligand end up bound to adjacent (1,2) atoms
of an L‐type ligand

The type of insertion observed in any given case depends on the nature of the 2e inserting ligand
• For example:  CO gives only 1,1 insertion 
ethylene gives only 1,2 insertion, in which the M and the X end up on adjacent atoms of
what was the 2e X‐type ligand
In general, η1 ligands tend to give 1,1 insertion and η2 ligands give 1,2 insertion

Enhancing insertion rates

• Steric bulk in the ligand set accelerates insertion, no doubt because the acetyl in the
LnM(COMe) product, occupying one coordination site, is far less bulky than the alkyl and
carbonyl, occupying two sites.
 • Lewis acids such as AlCl3 ,BF3 or H+ can increase the rate of migratory insertion by as
much as 108‐fold. resonance form.
CO insertion reactions
The most studied MI is CO insertion. CO shows a strong tendency to insert into metal–
alkyl bonds to give metal acyls.

Olefins usually inserts across a M−H bond and such insertions are of
relevance to the commercially important olefin polymerization process. In
certain cases the 1,2−insertions of olefins give species exhibiting agostic
insertions.
Alkene insertions reactions
Alkene insertion is common for M−H, but much less common for M−[Link] insertion of
coordinated alkenes into M−H bonds results in conversion of a π coordinated ligand (alkene) to a
σ bonded alkyl. Alkene insertions reaction
is a very important reaction because it gives alkyls and constitutes a key step in a variety of
catalytic reactions including alkene polymerization, perhaps the most commercially important
organometallic reaction.
• As η2‐ligands, alkenes give 1,2 insertion. This is the reverse of the familiar ‐elimination
reaction.
• Some insertion reactions are known to give agostic rather than classical alkyls, and probably
lie on the pathway for insertion into M−H bonds.
 • The position of equilibrium is decided by the thermodynamics of the particular system, and
depends strongly on the alkene involved. • For simple alkenes, such as ethylene, the equilibrium
tends to lie to the left (i.e., the alkyl  eliminates) but for alkenes with electron‐withdrawing
ligands (e g C F ) the alkyl is particularly stable, and the equilibrium lies entirely to the right;

β-Hydride elimination is a reaction in which a metal-alkyl centre is converted into

the corresponding metal-hydrideand alkene alkene. β-Hydride elimination can also
occur for many alkoxide complexes as well, It involves the transfer of a hydrogen
atom (formally a hydride, H-) from a carbon atom (β to the metal) to the metal
center, simultaneously forming a π bond in the ligand. This reaction is a
common decomposition pathway for metal alkyls and plays a significant role in

various catalytic cycles.

Requirements:
 β-hydrogen: The alkyl group must have a hydrogen atom on the carbon β to the
metal.
 Coordinative unsaturation: The metal center must have an open coordination site.
 Metal d-electrons: The metal center needs at least two d-electrons for backbonding
to stabilize the transition state.
 Syn coplanar geometry: The metal, α-carbon, β-carbon, and hydrogen must be in
the same plane
Consequences:
 Formation of metal hydride and alkene: The primary products are a metal hydride
and an alkene, formed via the transfer of the hydride and the creation of a π bond.
 Decomposition pathway for metal alkyls: β-hydride elimination can be a major
pathway for the decomposition of metal alkyl complexes.
 Key step in catalysis: It can be a crucial step in various catalytic cycles, such as
those involved in dehydrogenation, olefin polymerization, and olefin metathesis
 Factors influencing the reaction:
 Ligand dissociation: The presence of a labile ligand can create a vacant site,
facilitating β-hydride elimination.
 Metal center electronic structure: The availability of d-electrons and the ability to
form backbonds with the alkene influence the rate of elimination.
 Steric effects: The geometry of the complex and the steric environment around the
metal center can affect the ability to achieve the syn coplanar transition state.
 Distinction from α-elimination:
While β-hydride elimination involves a hydrogen on the β-carbon, α-
elimination involves the removal of a hydrogen from the α-carbon, leading to the
formation of a carbene complex.

A ligand substitution reaction involves the replacement of one or more ligands

in a coordination complex with other ligands. These reactions are fundamental
in inorganic and organometallic chemistry, and understanding their
mechanisms is crucial for synthesizing new compounds and understanding
their reactivity.

Associative Substitution
The associative substitution reaction is the inorganic analog of an
SN2 reaction. In associative ligand substitution, the incoming ligand (Y) forms
a new bond with the metal (M) before the bond to the leaving ligand (X)
breaks. The first step, formation of the new M-Y bond is generally rate-
determining. A typical mechanism for associative ligand substitution in both
octahedral and square planar complexes is shown in Figure 10.3.
In an octahedral complex the intermediate is 7 coordinate, so
associative ligand exchange in octahedral complexes is rare and only
favored with larger metal ions and ligands that are not sterically
demanding. In contrast, ligand substitution in square planar complexes
almost always occurs via an associative mechanism, involving
approach of the incoming ligand to the open coordination sites above
or below the plane. Let’s begin with the kinetics of the reaction. How
can we spot an associative mechanism in experimental data, and what
are some of the consequences of this mechanism?

Dissociative Substitution
The associative substitution mechanism is unlikely for 6 coordinate
complexes. For octahedral complexes dissociative substitution mechanisms
involving 5 coordinate intermediates are more likely. In a slow step, the
departing ligand leaves, generating a coordinatively unsaturated 5
coordinate intermediate. The incoming ligand then enters the coordination
sphere of the metal to generate the product. We’ll focus on the kinetics of
the reaction and the nature of the unsaturated intermediate (which
influences the stereochemistry of the reaction). The reverse of the first step,
re-coordination of the departing ligand (rate constant k–1), is often
competitive with dissociation.

Interchange Substitution
Real life chemical reactions don't always fall neatly into one of the categories
above. In some cases the M-X bond can break and the M-Y bond can form
simultaneously. An interchange reaction is a concerted reaction without an
intermediate. The transition state is a species where the bond to Y is partially
formed and the bond to X is partially broken as seen in Figure 10.3.6. If the
new M-Y bond forms faster than the M-X bond breaks tat is an associative
interchange (IA) reaction and if the M-X bond breaks faster than the new M-Y
bond forms that is a dissociative interchange reaction (ID)

n which the platinum is oxidized from +4 to +6 with the formation of two additional bonds. One
important complex that functions as a catalyst is Wilkinson’s catalyst, Rh(Pϕ3)3Cl (where
ϕ = phenyl, C6H5). A very significant property of this complex is that it undergoes an oxidative
addition reaction with hydrogen.
(22.6)Rh(Pϕ3)3Cl+H2→Rh(Pϕ3)3ClH2

The product of the reaction has the structure

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in which the rhodium is formally +3 with the hydrogen considered as H−. In many oxad
reactions, H2 adds as two H− ions in cis positions as if a hydrogen molecule approached the
complex and added as atoms while the H−H bond simultaneously breaks. This is also true of
gaseous HCl, which usually adds H and Cl in cis positions. On the other hand, in aqueous
solutions where the HCl is largely dissociated, the addition is not restricted to cis positions, so
the product contains H and Cl atoms in both cis and trans positions. The stereochemistry of the
product depends on the solvent, and if the solvent has considerable polarity, the product consists
of a mixture of cis and trans isomers. When the solvent is essentially nonpolar, the product
contains hydrogen and halide in cis positions.
Another important complex is trans-[Ir(Pϕ3)2COCl], which is known as Vaska’s compound. This
complex undergoes a large number of oxidative addition reactions because Ir+ is easily oxidized
to Ir3+ and that ion forms many stable octahedral complexes. When CH3I is added, the octahedral
product contains CH3 and I in trans positions with the other ligands in a plane as shown below.

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This oxad reaction is first order in both complex and CH3I, and the entropy of activation is large
and negative. It is believed that the reaction goes through an ionic transition state in which
CH3 adds to a pair of electrons on Ir followed by the attachment of I− in the trans position.
The nature of the oxad reaction requires that the following conditions generally apply.
1.

It must be possible to change the oxidation state of a metal. Normally, the metal changes
oxidation state by 2 units, but two metal atoms can change by 1 unit each as shown in
Eqns (22.10) and (22.11).
2.

The metal must be able to increase its coordination number by 2 except in cases like that
shown in Eqns (22.10) and (22.11).
3.

Diatomic molecules such as H2, Cl2, or HCl add in cis positions when reacting as gases or
as solutions in nonpolar solvents that do not assist in separating the molecules. In polar
solvents, molecules that dissociate are not restricted to entering in cis positions.
One of the most interesting complexes that also figures prominently in catalytic processes is
Co(CN)53−. Because Co2+ is a d7 ion, forcing the pairing of the electrons leaves one orbital
occupied by only one electron and another empty. This makes possible the formation
of dsp3 hybrid orbitals, and the complex is trigonal bipyramidal as expected. It is the singly
occupied orbital that gives the complex its unusual character, the ability to behave as a free
radical. In fact, Co(CN)53− undergoes many reactions that are similar to those of other radicals. As
expected, there is a coupling reaction, which can be shown as
(22.7)2Co(CN)53−⇆Co2(CN)106−

Numerous other reactions of Co(CN)53− have been observed with a wide variety of substances.
For example, the reaction with alkyl halides can be shown as follows:
(22.8)RX+Co(CN)53−→Co(CN)5X3−+R·

(22.9)R·+Co(CN)53−→RCo(CN)53−

These reactions are typical oxad processes because the cobalt is formally converted from +2 to
+3. Many other molecules such as H2, H2O2, Br2, O2, C2H2, etc., are split in a homolytic manner
during reactions with Co(CN)53−. For example, the reaction with hydrogen is illustrated in the
following equation:
(22.10)H2+2Co(CN)53−→2HCo(CN)53−

These reactions show the tendency of the metal to behave as a radical as a result of having an unpaired
electron and a vacant position where a sixth ligand may be added.

The [Co(CN)5]3− complex is an effective catalyst for some reactions, particularly

the isomerization of alkenes. Newer and more efficient catalysts have been developed for some
of the processes, but the catalytic behavior of the pentacyanocobalt(II) ion is also significant
from a historical perspective. In reactions such as that shown in Eqn (22.10), two Co2+ ions
increase one unit in oxidation state instead of the more common situation in which one metal
ion increases by two units in oxidation state. The cobalt complex also reacts with CH3I, Cl2, and
H2O2, which are indicated as X−Y in the equation
(22.11)2[Co(CN)5]3−+X−Y→[XCo(CN)5]3−+[YCo(CN)5]3−

Mechanistic studies have shown that the reaction represented in Eqn (22.10) is a one-step
process that follows the rate law
(22.12)Rate=k[H2][Co(CN)53−]2

whereas the reaction of [Co(CN)5]3− with H2O2 follows a free radical mechanism. Other aspects of
the chemistry of [Co(CN)5]3− will be illustrated later in this chapter.
A different type of oxidative addition involves the transfer of a hydrogen atom from a
coordinated group to the metal atom followed by (or simultaneous with) a change in bonding
mode to the ligand from which the hydrogen atom came. This is illustrated in the following
example, in which ϕ is a phenyl group, C6H5.

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(22.13).
A reaction of this type is sometimes referred to as orthometallation because it is from
the ortho position that the hydrogen is transferred to the metal.
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Chapter
Fundamentals
2007, Comprehensive Organometallic Chemistry IIIR.N. Perutz, T. Braun

[Link].1 Oxidative addition

Classical oxidative addition of a fluorinated alkane at a transition metal center still remains
elusive. However, such a step is conceivable in catalytic cross-coupling reactions of primary
alkyl fluorides.55 The reactions of lanthanoid cations with CH3F to form LnF+ and ·CH3 have been
described as oxidative additions, but do not conform to our definition of oxidative addition.56,57

Vaska’s complex (Figure 1), the discovery of which is credited to Angoletta in 1958 but
named after the Estonian-American chemist Lauri Vaska after his extensive characterisation
in 1962, is an air-stable 16-electron square planar iridium (I) complex that readily undergoes
oxidative addition with a number of oxidants, acids and electrophiles (e.g. CO, SO2,Cl2 , CH3I)
generating an 18-electron octahedral Ir(III) species (Figure 2).Vaska’s complex also binds
reversibly to molecular oxygen in a ‘side-on’ fashion as opposed to the ‘end-on’ binding
found with the iron complex haemoglob
 Beta-hydride elimination is a fundamental reaction in organometallic chemistry
where a metal-alkyl complex is converted into a metal-hydride and an
alkene. This process involves the transfer of a hydrogen atom (hydride) from
the carbon atom that is beta (β) to the metal center to the metal itself,
simultaneously forming a double bond (alkene) between the carbon atoms.
Here's a more detailed explanation

Beta-hydride elimination is a fundamental reaction in organometallic chemistry

where a metal-alkyl complex is converted into a metal-hydride and an
alkene. This process involves the transfer of a hydrogen atom (hydride) from
the carbon atom that is beta (β) to the metal center to the metal itself,
simultaneously forming a double bond (alkene) between the carbon atoms.
Here's a more detailed explanation:

Key Features:
 Metal-Alkyl Complex:
The reaction starts with an organometallic compound where an alkyl group (a carbon
chain with hydrogens) is bonded to a metal center.
 β-Hydrogen:
The hydrogen atom involved in the elimination must be on the carbon atom that is
adjacent to (β to) the metal-bound carbon.
 Metal Hydride and Alkene Formation:
The β-hydrogen migrates to the metal, forming a metal-hydride bond, while the
remaining carbon atoms form a double bond (alkene).
 Coordination Site:
The metal center must have an empty coordination site (an available orbital) to accept
the hydride and accommodate the alkene.
 Reversibility:
Beta-hydride elimination is often reversible, and its microscopic reverse is called olefin
insertion.
Importance:
 Key Step in Catalysis:
Beta-hydride elimination is a crucial step in many catalytic cycles, such as in olefin
polymerization and various cross-coupling reactions.
 Stability/Reactivity:
The ease of beta-hydride elimination can significantly affect the stability and reactivity
of metal alkyl complexes.
 Product Formation:
It can be a desirable step in some catalytic processes (e.g., alkene synthesis) but also
a source of undesired side reactions in others (e.g., polymerization).
Example:
Consider a metal complex with an ethyl group (CH₃CH₂-) bonded to the
metal. If the metal has an empty coordination site, the ethyl group can
undergo beta-hydride elimination, forming a metal hydride and ethylene
(CH₂=CH₂).
In essence, beta-hydride elimination is a fundamental reaction that transforms
a metal-alkyl complex into a metal-hydride and an alkene, playing a vital role
in various chemical transformations, including catalysis.

Migratory insertion
Migratory insertion in organometallic chemistry is a reaction where two ligands
on a metal complex combine, resulting in a new bond formation and a vacant
coordination site. It's a type of insertion reaction where a ligand migrates to an
unsaturated ligand coordinated to the metal center. This reaction is crucial in
various catalytic processes, particularly in transformations involving carbon
monoxide (CO) and alkenes.
Migratory insertion in organometallic chemistry is a reaction where two ligands
on a metal complex combine, resulting in a new bond formation and a vacant
coordination site. It's a type of insertion reaction where a ligand migrates to an
unsaturated ligand coordinated to the metal center. This reaction is crucial in
various catalytic processes, particularly in transformations involving carbon
monoxide (CO) and alkenes.

Key aspects of migratory insertion:

 Ligand Migration:
One ligand (often an alkyl or hydride) moves to the unsaturated ligand, effectively
inserting itself into the bond between the metal and the unsaturated ligand.
 Vacant Coordination Site:
 The migration of the ligand creates a vacant coordination site on the metal center.
 Cis-Ligands:
Migratory insertion typically occurs between ligands that are positioned cis to each
other on the metal center.
 Reversibility:
The reaction can be reversible, with the inserted ligand potentially migrating back to its
original position.
 Examples:
Common examples include CO insertion (carbonylation) and alkene insertion (which is
the basis for polymerization catalysts).
 No Change in Oxidation State:
The metal's oxidation state generally remains unchanged during the migratory
insertion process.
Mechanism:
1. Coordination: The unsaturated ligand (e.g., CO, alkene) coordinates to the metal
center.
2. Migration: A ligand (e.g., alkyl, hydride) migrates to the coordinated unsaturated ligand,
forming a new bond.
3. Vacancy: A vacant coordination site is created on the metal.
Examples:
 CO Insertion:
A common example is the insertion of CO into a metal-alkyl bond, forming a metal-acyl
complex.
 Alkene Insertion:
Alkene insertion is a key step in many polymerization reactions, where the alkene
inserts into a metal-carbon bond, extending the polymer chain.
 β-Hydride Elimination:
The reverse of migratory insertion, where a beta-hydride ligand eliminates from the
metal center, is known as β-hydride elimination.
Factors Influencing Migratory Insertion:
 Ligand Nature:
 The steric and electronic properties of the ligands can influence the rate and direction
of insertion.

 Metal Center:
The metal's electronic configuration and its ability to coordinate and activate the
ligands play a crucial role.
 Reaction Conditions:
Temperature, pressure, and solvent can affect the reaction rate and equilibrium.