Reaction mechanism in coordination

compounds

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 Ligand substitution reactions

• A proposed mechanism must be consistent with all

experimental facts.

• A mechanism cannot be proven, since another

mechanism may also be consistent with the
experimental data.

• Need to distinguish between Kinetically Inert and

Labile Complexes

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• Kinetically labile complexes are metal complexes that
1
undergo reactions with t 2  1 min .
• Special techniques are required for collecting data
during such reactions, as they may appear to be
finished within the time of mixing.

• Kinetically inert complexes have a reaction which takes

significantly longer than 1 min.
• They are slow enough to be studied by classical
techniques where the reagents are mixed and changes
in absorbance, Ph, gas evolution, e.t.c are followed
directly by the observer.

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 • No connection between the thermodynamic
stability of a complex and its lability towards
substitution.

• E.g. values for ΔhydG⁰ for Cr3+ and Fe3+ are almost
equal, yet [Cr(H2O)6]3+ undergoes substitution
slowly and [Fe(H2O)6]3+ (high-spin d5) rapidly.

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 •The formation constant of [Hg(CN)4]2- is greater than
that of [Fe(CN)4]4-, the Hg(II) complex rapidly
exchanges [CN]- with isotopically labeled cyanide,
while exchange is extremely slow for [Fe(CN)4]4-.

•Kinetic inertness of d3 and low-spin d6 octahedral

complexes is in part associated with crystal field
effects.

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 Types of Substitution Mechanisms
• Two extreme mechanistic possibilities may be
considered for any ligand substitution process or for
any single step in a series of substitution reactions.

a) Dissociative (D) mechanism, in which the ligand to

be replaced dissociates from the metal center, the
vacancy in the coordination sphere then being
taken by the new ligand

i.e the intermediate has a lower coordination number

than the starting complex.
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• An example is

• The first step of the mechanism (dissociation of the

leaving group) is the rate determining step.

• The mechanism is comparable to the SN1 mechanism

in organic systems, because the formation of the
intermediate with reduced coordination number is
unimolecular, as well as rate determining.
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b) Addition-elimination or Associative (A) mechanism,
in which the intermediate has a higher
coordination number than the starting complex.

 The incoming ligand, Y, attacks the original

complex directly to form a seven coordinate
intermediate in the rate determining step.

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 • The rate determining step is bimolecular.

• Unfortunately, the two extreme mechanisms are

just that extremes and the observed mechanisms
are seldom so simple.

• Instead of a 5 or 7-coordinate intermediate, a

transition state may be reached in which some
degree of bond breaking accompanies a given
degree of bond making.
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 •The interchange of the ligands X and Y would be
accomplished mostly by breaking the bond to the
leaving group (interchange dissociative-Id).

•OR by making the bond to the entering group

(interchange associative-Ia).

•But in each case both ligands are bound to the metal

to one extent or another.
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• In these reaction mechanisms, a two- step pathways
and an intermediate are involved.

• An intermediate occurs at a local energy minimum; it

can be detected and, sometimes, isolated.

• A transition state at an energy maximum, and

cannot be isolated.

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 • In most metal complex substitution pathways, bond
formation between the metal and entering group is
thought to be concurrent with bond cleavage
between the metal and leaving group.

• This is called the interchange (I) mechanism.

ML5X + Y Y---ML5---X ML5Y + X

entering transition Leaving
group state group
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• In an I mechanism, there is no intermediate but
various transition states are possible. Two types of
interchange mechanisms can be identified:

• Dissociative interchange (Id), in which bond breaking

dominates over bond formation;

• Associative interchange (Ia), in which bond formation

dominates over bond breaking.

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 •In an Ia mechanism, the reaction rate shows a
dependence on the entering group. In an Id
mechanism, the rate shows only a very small
dependence on the entering group.

•An interchange (I) mechanism is concerted process

in which there is no intermediate species with a
coordination number different from that of the
starting complex.

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 Substitution in Square Planar Complexes

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 Electron transfer reactions

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 Oxidation-reduction Reactions
These are reactions which involve transfer of
electrons from one complex to another.

Mechanistically they are of two types:

a) Outer-sphere mechanism and
b) Inner-sphere mechanism

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 Inner-sphere mechanism

• Inner-sphere mechanism are those in which electron

transfer takes place through a bridging atom or
group which is common to the coordination spheres
of both complexes.

• They occur between reactants which are labile to

substitution processes.

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•The inner-sphere mechanism was first confirmed for the
reduction of the nonlabile complex [CoCl(NH3)5]2+ by Cr2+(aq)
(Scheme 1).

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 Evidences to support Inner-Sphere Mechanism
in Scheme 1

Observation 1

Addition of 36Cl- to the solution did not lead to the

incorporation of any of the isotope into the Cr(III)
product.
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 Discussion

i. It means that the Cl- attached to the Cr(III) on the

product side has been received from the reactant
itself and not from any external sources.

ii. It further indicates that for the transfer of Cl- from

Co(III) to Cr(III), bridge formation must have
occurred as indicated in the inner-sphere
mechanism otherwise some amount of product
with 36Cl- would also have formed.
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 Observation

The rate of this reaction (Scheme 1) is much faster

than reactions which involves removal of Cl- from
nonlabile Co(III) or addition of Cl- into the nonlabile
[Cr(H2O)6]3+ complex.

Discussion

It means that the presence of Cl– in close proximity as

in the case of inner-sphere mechanism, facilitates the
transfer process and therefore enhances the rate of
reaction.
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 Conclusion

•These observations suggest that Cl has moved

directly from the coordination sphere of one complex
to that of the other during the reaction.

•The Cl attached to Co(III) can easily enter into the

labile coordination sphere of [Cr(H2O)6]2+ to produce
a bridged intermediate.

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 Outer-Sphere Mechanism

•Outer-Sphere Mechanism: In an outer-sphere

mechanism, the complexes come into contact
without sharing a bridging ligand and the electron
tunnels from one metal atom to the other.

•It is the one occurring between inert complexes; in

these, substitution reactions are slower than
electron transfer reactions.

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 Outer sphere reactions

• The reactions have a rate law that is first order in

both reactants.

• Usually both reactants are inert.

• Many examples of such reactions are found in

electron exchange reactions which do not represent
overall chemical reactions
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• The rate of this exchange can be studied by labeling
one of the complexes with a radioactive isotope of
iron.

• [Fe*(CN)6]4- + [Fe(CN)6]3- [Fe*(CN)6]3- + [Fe(CN)6]4-

• The hexacyanoferrate(III) is a low-spin d5 system and

hexacyanoferrate(II) is a low-spin d6 system, both of
which are inert to substitution and hence the loss or
exchange of cyanide ions is very small.
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 •The electron exchange rate is very fast that the
possibility of a bridged activated complex being
important is ruled out since the mere formation of
such a complex amounts to a substitution process.

•The outer-sphere mechanism is also the correct one

when no ligand is capable of serving as a bridging
ligand.

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• There are two steps in this mechanism

A pre-equilibrium step characterized by the constant

Kos, in which an outer sphere complex(or ion pair) is
formed.

 [Fe(CN)6]4- + [IrCl6]2- ↔ [Fe(CN)6]4-/ [IrCl6]2- ........Kos

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 •This outer-sphere complex or ion pair between the
reactants brings them to be within the internuclear
separation required for electron transfer.

The electron transfer step, takes place within this

outer sphere complex, only after metal ligand bond
lengths have been altered enough to allow the
electron transfer to take place adiabatically (i.e.
without further change in energy).

 [Fe(CN)6]4-/ [IrCl6]2-→ [Fe(CN)6]3- + [IrCl6]3- …….Ket

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 • The electron transfer reaction should be
adiabatic, because electron motion should be
faster than nuclear motion

• In other words, the electron transfer takes place

quickly, once internuclear distances have become
appropriately adjusted.
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 Rate constants for some self exchange reactions that
proceed via outer-sphere mechanism

Reactants Rate constants (L/mol/s)

[Fe(bipy)3] 2+, [Fe(bipy)3] 3+
[Mn(CN)6]3-, [Mn(CN)6]4-
[Mo(CN)8]3-, [Mn(CN)8]4- 104-106
[W(CN)8]3-, [Mn(CN)8]-
[IrCl6]2-, [IrCl6]3-
[Os(bipy)3]2+, [Os(bipy)3]3+
[Fe(CN)6]3-, [Fe(CN)6]4- 7.4 X 102
[MnO4]-, [MnO4]- 3 X 103
[Co(en)3]2+, [Co(en)3]3+ ≈ 10-4
[Co(NH3)6]2+, [Co(NH3)6]3+
[Co(C2O4)3]3- , [Co(C2O4)3]4-
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