COORDINATION CHEMISTRY

Reactions of Complexes
 Coordination Chemistry
Reactions of Complexes
Coordination chemistry is not the sole preserve of d metals. Coordination
chemistry is applied to all metals regardless of the block to which they
belong. However, there are special features of each block, and we shall
point them out

Ligand substitution reactions

The most fundamental reaction a complex can undergo is ligand substitution, a

reaction in which one Lewis base displaces another from a Lewis acid:
Y + MX → MY + X

This class of reaction includes complex formation reactions, in which the

leaving group, the displaced base X, is a solvent molecule and the entering
group, the displacing base Y, is some other ligand

An example is the replacement of a water ligand by Cl:

[Co(OH2)6]2+(aq) + Cl−(aq) → [CoCl(OH2)5]+(aq) + H2O(l)
 Coordination Chemistry
Reactions of Complexes - Rates of ligand substitution
The rates of substitution reactions span a very wide range and correlate
with the structures of the complexes; complexes that react quickly are
called labile, those that react slowly are called inert or nonlabile.
Rates of reaction are as important as equilibria in coordination chemistry.

The well-known isomers of the ammines of Co(III) and Pt(II) could not have
been isolated if ligand substitutions and interconversion of the isomers had
been fast.

But what determines whether one complex will survive for long
periods whereas another will undergo rapid reaction?
 Coordination Chemistry
Reactions of Complexes - Rates of ligand substitution
The rate at which one complex converts
into another is governed by the height
of the activation energy barrier that
lies between them.

Kinetically controlled stereoselectivity. Note

that ∆‡GS < ∆‡GR, so the minor isomer
reacts faster than the major isomer

Thermodynamically unstable complexes that survive for long periods

(at least 1 minute) are commonly called ‘inert’ or nonlabile.
Complexes that undergo more rapid equilibration are called labile.
Labile complex: [Ni(OH2)6]2 (has a half-life of the order of msec before the
H2O is replaced by another H2O molecule or a stronger base)

Nonlabile complex: [Co(NH3)5(OH2)]3+, in which H2O survives for several minutes

as a ligand before it is replaced by a stronger base
 Coordination Chemistry
Reactions of Complexes - Rates of ligand substitution
The rate at which one complex converts into another is governed by the
height of the activation energy barrier that lies between them.
Thermodynamically unstable complexes that survive for long periods (at
least 1 minute) are commonly called ‘inert’ or nonlabile. Complexes that
undergo more rapid equilibration are called labile.

Years Nanosecons

Characteristic lifetimes for exchange of water molecules in aqua

complexes
 Coordination Chemistry
Reactions of Complexes - Rates of ligand substitution
The rate at which one complex converts into another is governed by the
height of the activation energy barrier that lies between them.
Thermodynamically unstable complexes that survive for long periods (at
least 1 minute) are commonly called ‘inert’ or nonlabile. Complexes that
undergo more rapid equilibration are called labile.
 Coordination Chemistry
Reactions of Complexes - Rates of ligand substitution
Kinetically inert and labile complexes
Metal complexes that undergo reactions with t" 1/2 ≤ 1 min are described as
being kinetically labile. If the reaction takes significantly longer than this,
the complex is kinetically inert.

The kinetic changes are associated to modifications in the energy of

the activated complex
Kinetic aspects "→ Labil/Inert

The thermodynamic changes are associated to modifications in the

energy between products and reactants
Thermodynamic aspects "→ Stable/Unstable
 Coordination Chemistry
Reactions of Complexes - Rates of ligand substitution
Kinetically inert and labile complexes
There is no connection between the thermodynamic stability of a complex
and its lability towards substitution

Inert Inert
Unstable Stable
Labil
Stable

Labil
Unstable
 Coordination Chemistry
Reactions of Complexes - Rates of ligand substitution
Kinetically inert and labile complexes
There is no connection between the thermodynamic stability of a complex
and its lability towards substitution

Stable, labil or inert?

A thermodynamically stable compound can be inert or label

Complex [Fe(H2O)6]2+ [Cr(H2O)6]3+

Bond Energy (kJ/mol) 116 122
Interchange K (s-1) 10-6 102

Both complexes have similar bond energies, however, the

differences in the interchange rates make the reactions of
iron compound practically spontaneous. On the other
hand, the reactions of Cr(III) derivative could take days.
 Coordination Chemistry
Reactions of Complexes - Rates of ligand substitution
Kinetically inert and labile complexes
The distinction is relevant when product A forms faster than product B because
the activation energy for product A is lower than that for product B, yet
product B is more stable

In such a case A is the kinetic

product and is favored under kinetic
control and B is the thermodynamic
product and is favored under
thermodynamic control

The reaction can be kinetically or

thermodynamically controlled
modifying the reaction conditions
A such as temperature, pressure or
solvent
B
 Coordination Chemistry
Reactions of Complexes - Rates of ligand substitution
Metal complexes that have no additional factor to provide extra
stability (for instance, the LFSE and chelate effects) are among the most
labile. Any additional stability of a complex results in an increase in
activation energy for a ligand replacement reaction and hence decreases
the lability of the complex

A second generalization is that very small ions are often less labile
because they have greater M-L bond strengths and it is sterically very
difficult for incoming ligands to approach the metal atom closely.
 Coordination Chemistry
Reactions of Complexes - Rates of ligand substitution
Some further generalizations are as follows:
 Coordination Chemistry
Reactions of Complexes - Rates of ligand substitution
Simple examples are the preparation of [Co(NH3)6]3+ and [Rh(NH3)6]3+:

[O]
[CoCl4]2- + NH3(excess) ⟶ [Co(NH3)6]2+ ⟶ [Co(NH3)6]3+

[O] = air or H2O2

[RhCl3]H2O + NH3(excess) ⟶ [Rh(NH3)6]3+

The reaction is carried out in a sealed tube under
high temperature and pressure
 Coordination Chemistry
Reactions of Complexes - Rates of ligand substitution
The natures of the ligands in the complex also affect the rates of
reactions. The identity of the incoming ligand has the greatest effect, and
equilibrium constants of displacement reactions can be used to rank
ligands in order of their strength as Lewis bases.

Representative timescales of chemical and physical processes

 Coordination Chemistry
Reactions of Complexes - Rates of ligand substitution
For kinetic considerations, we replace the equilibrium concept of
basicity by the kinetic concept of nucleophilicity, the rate of attack on a
complex by a given Lewis base relative to the rate of attack by a
reference Lewis base. The shift from equilibrium to kinetic considerations
is emphasized by referring to ligand displacement as nucleophilic
substitution

Equilibrium Lewis base

Kinetic Nucleophile

Spectator ligands
Ligands other than the entering and leaving
groups, and play a significant role in controlling
the rates of reactions
 Coordination Chemistry
Reactions of Complexes - The classification of mechanisms
The mechanism of a reaction is the sequence of elementary steps by
which the reaction takes place
The first stage in the kinetic analysis of a reaction is to
study how its rate changes as the concentrations of reactants
are varied

Identification of rate laws

An example is the replacement of a water ligand by Cl:

[Ni(OH2)6]2+ + NH3 → [Ni(NH3)(OH2)5]2+ + H2O
Rate = "kr[Ni(OH2)2+
6 ][NH3]
The brackets denote molar concentration

Rate-determining step: the slowest elementary step of the reaction

that dominates the overall reaction rate and the overall rate law
 Coordination Chemistry
Reactions of Complexes - The classification of mechanisms
The mechanism of a reaction is the sequence of elementary steps by
which the reaction takes place

Nucleophilic substitution reaction: Association, dissociation,

and interchange
A dissociative mechanism, denoted D, is a reaction sequence in
which an intermediate of reduced coordination number is formed by
the departure of the leaving group

The intermediate W(CO)5 is rapidly

captured by the solvent
 Coordination Chemistry
Reactions of Complexes - The classification of mechanisms
The mechanism of a reaction is the sequence of elementary steps by
which the reaction takes place

Nucleophilic substitution reaction: Association, dissociation,

and interchange
An associative mechanism, denoted A, involves a step in which an
intermediate is formed with a higher coordination number than the
original complex

This mechanism plays a role in many

reactions of square-planar Au(III), Pt(II),
Pd(II), Ni(II), and Ir(I) d8 complexes
 Coordination Chemistry
Reactions of Complexes - The classification of mechanisms
The mechanism of a reaction is the sequence of elementary steps by
which the reaction takes place
Nucleophilic substitution reaction: Association, dissociation,
and interchange

An interchange mechanism, denoted I, takes place in one step

The leaving and entering groups

exchange in a single step by
forming a transition state but not
The interchange mechanism is
a true intermediate
common for many reactions of six-
coordinate complexes
 Coordination Chemistry
Reactions of Complexes - The classification of mechanisms
The mechanism of a reaction is the sequence of elementary steps by
which the reaction takes place
Nucleophilic substitution reaction: Association, dissociation,
and interchange

The distinction between the A and I mechanisms hinges on

whether or not the intermediate persists long enough to be
detectable

One type of evidence is the isolation of an intermediate in another related

reaction or under different conditions

These complexes are the

intermediates involved when
CN- exchanges with the
s q u a r e - p l a n a r
tetracyanidonickelate(II) ion
 Coordination Chemistry
Reactions of Complexes - The rate-determining step
The rate-determining step is classified as associative (a) or dissociative
(d) according to the dependence of its rate on the identity of the entering
group

The step is called associative if its rate depends strongly on the

identity of the incoming group
 Coordination Chemistry
Reactions of Complexes - The rate-determining step
Associatively activated pathways

The use of I −instead of Br −increases the rate constant by an order of

magnitude

Associative mechanism
associatively activated
Aa

A reaction with an associative mechanism

(A) will be associatively activated (a) if the
attachment of Y to the initial reactant MLnX
is the rate-determining step

the intermediate MLnXY would not be detected

 Coordination Chemistry
Reactions of Complexes - The rate-determining step
Associatively activated pathways

The step is called associative if its rate depends strongly on the

identity of the incoming group

Dissociative mechanism
associatively activated
Da

A reaction with a dissociative mechanism

(D) is associatively activated (a) if the
attachment of Y to the intermediate MLn is
the rate-determining step
 Coordination Chemistry
Reactions of Complexes - The rate-determining step
Dissociatively activated pathways

The rate-determining step is called dissociative if its rate is largely

independent of the identity of Y

It is found that replacement of NH3 by pyridine in this reaction changes

the rate by at most a few per cent

Associative mechanism
dissociatively activated
Ad

A reaction with an associative mechanism

(A) is dissociatively activated (d) if the the
loss of X from the intermediate YMLnX is the
rate-determining step
 Coordination Chemistry
Reactions of Complexes - The rate-determining step
Dissociatively activated pathways

The rate-determining step is called dissociative if its rate is largely

independent of the identity of Y

A reaction with a dissociative mechanism (D) is dissociatively activated

(d) if the initial loss of X from the reactant MLnX is the rate-determining
step

Dissociative mechanism
dissociatively activated
Dd

the intermediate MLn would not be detected

 Coordination Chemistry
Reactions of Complexes - The rate-determining step
The rate-determining step is classified as associative (a) or dissociative
(d) according to the dependence of its rate on the identity of the entering
group

A reaction that has an interchange mechanism (I) can be either

associatively (Ia) or dissociatively activated (Id)

In both cases, the

intermediate would
not be detected

In an Ia mechanism, the rate of reaction In an Id reaction the rate of reaction

depends on the rate at which the M"⋯Y depends on the rate at which the M"⋯X
bond forms bond breaks
 Coordination Chemistry
Reactions of Complexes - The rate-determining step
The rate-determining step is classified as associative (a) or dissociative
(d) according to the dependence of its rate on the identity of the entering
group

In summary…
 Coordination Chemistry
Ligand substitution in square-planar complexes
The vast majority of square-planar transition metal complexes are d8
 Coordination Chemistry
Ligand substitution in square-planar complexes
Complexes with d8 configuration are generally tetra-coordinate with square-
planar geometry

A) Nature of the entering group

B) Nature of the ligands in the metal complex

- ligands trans to the leaving group

- Ligands cis to the leaving group

- Steric effects

C) Nature of the metallic ion

D) Nature of the leaving group

 Coordination Chemistry
Ligand substitution in square-planar complexes
Rate of a reaction can be affected by several factors

Few example are these: Au(III), Pt(II), Pd(II), Ni(II), Ir(I), Rh(I), Co(I)

Ni(II) complexes can display tetrahedral or even octahedral geometry

Ligand substitution reactions are normally studied on Pt(II)

complexes because…

a) they are more stable than Rh(I) and Ir(I) derivatives

b) they only display square-planar geometry
c) The reaction rates are occur on a timescale that is very
amenable to investigation

Pt(II) : Pd(II) : Ni(II) are in the order of 1 : 105 : 107

 Coordination Chemistry
Ligand substitution in square-planar complexes
We might expect an associative mechanism of ligand exchange because
square-planar complexes are sterically uncrowded (they can be considered
as octahedral complexes with two ligands missing)

There are several pathways for the incorporation of ligands on square-

planar complexes:
1. Nucleophilic substitution
2. Electrophilic substitution
3. Oxidative addition followed by reductive elimination

Oxidative addition Nucleophilic substitution

Cl2 N 3-
[PtClMe(PMe2Ph)2Cl2] [PtClMe(PMe2Ph)2] [Pt(N3)Me(PMe2Ph)2] + Cl-

HgCl2

[Pt(PMe2Ph)2Cl2] + MeCl [PtCl2(PMe2Ph)2] + MeHgCl

Oxidative addition Electrophilic substitution
 Coordination Chemistry
Ligand substitution in square-planar complexes
The elucidation of the mechanism of the substitution of square-planar
complexes is often complicated by the occurrence of alternative pathways.
Let us consider the following reaction:

If the reaction is first order in

the complex and independent rate = kr,1[PtCl(dien )+ ]
of the concentration of I-:

If the reaction is first order in

the complex and first order in rate = kr,2[PtCl(dien )+ ][I −
]
the incoming group:

If both reaction pathways

rate = (kr,1 + kr,2[I −
])[PtCl(dien )+ ]
occur at comparable rates
 Coordination Chemistry
Ligand substitution in square-planar complexes
The nucleophilicity of the entering group
The nucleophilicity of an entering group is expressed in terms of the
nucleophilicity parameter (n Pt) defined in terms of the substitution
reactions of a specific square-planar platinum complex:
trans-[PtCl2(py)2] + Y ⟶ trans-[PtClY(py)2] + Cl-
Cl Y
MeOH
N Pt N + Y N Pt N + Cl-

Cl Cl

Nucleophilicity parameter:

where kr,2 (Y) is the second-order rate constant for the reaction and
o
kr,2 is the rate constant for the same reaction with the reference
nucleophile methanol
 Coordination Chemistry
Ligand substitution in square-planar complexes
The nucleophilicity of the entering group

Two main features:

1. The rate constants span nearly

nine orders of magnitude.

2. The nucleophilicity of the

entering group towards Pt
appears to correlate with soft
Lewis basicity with Cl- < I-, O <
S, and NH3 < PR3

A selection of n" Pt values

for a range of nucleophiles
towards trans-[PtCl2(py)2]
 Coordination Chemistry
Ligand substitution in square-planar complexes
The nucleophilicity of the entering group
When the complex itself is varied we find that the reaction rates show a
range of different sensitivities towards changes in the entering group

To express this range of sensitivities we rearrange this equation:

into o
where C = log kr,2

If we consider the general reaction [PtL3X] + Y → [PtL3Y] + X, then the

nucleophilicity parameter can be expressed as

Where the nucleophilic discrimination factor (S) characterizes the

sensitivity of the rate constant to the nucleophilicity parameter
 Coordination Chemistry
The nucleophilicity of the entering group

The straight line obtained for

trans-[PtCl2(PEt3)2] (red circles) is
steeper than that for reactions
with cis-[PtCl2(en)] (blue squares)

S is larger for the former reaction,

which indicates that the rate of
the reaction is more sensitive
to changes in the nucleophilicity of
the entering group

The slope of the straight line obtained

by plotting logk" r,2 (Y) against the
nucleophilicity parameter "n Pt(Y)
 Coordination Chemistry
Excercise

The second-order rate constant for the reaction of I- with trans-[PtCl(CH3)

(PEt3)2] in methanol at 30 ºC is 40 dm3 mol-1 s-1. The corresponding
reaction with N3- has k2 = 7.0 dm3 mol-1 s-1. Estimate S and C for the
reaction given the n Pt values of 5.42 and 3.58, respectively, for the two
nucleophiles
 Coordination Chemistry
Excercise

The second-order rate constant for the reaction of I- with trans-[PtCl(CH3)

(PEt3)2] in methanol at 30 ºC is 40 dm3 mol-1 s-1. The corresponding
reaction with N3- has k2 = 7.0 dm3 mol-1 s-1. Estimate S and C for the
reaction given the n Pt values of 5.42 and 3.58, respectively, for the two
nucleophiles

To determine S and C, we need to use the two pieces of information to set up

and solve two simultaneous equations based on the equation and the following
substitution of the two values of n Pt into equation gives

1.60 = 5.42S + C (for I-)

0.85 = 3.58S + C (for N3- )

Solving these two simultaneous equations gives S = 0.41 and C = -0.62. The
value of S is fairly small, showing that the discrimination of this complex
among different nucleophiles is not great.
 Coordination Chemistry
Ligand substitution in square-planar complexes
The shape of the transition state
Careful studies of the variation of the reaction rates of square-planar
complexes with changes in the composition of the reactant complex
and the conditions of the reaction help to elucidate the general shape
of the transition state

The Trans Effect

The spectator ligands T that are trans to the leaving group in square-
planar complexes influence the rate of substitution

A strong σ -donor ligand or π -

acceptor ligand greatly accelerates
substitution of a ligand that lies in
the trans position
 Coordination Chemistry
Ligand substitution in square-planar complexes
The Trans Effect
The trans effect arises from two separate influences: one arising in the
ground state and the other in the transition state itself

The trans influence is the extent to which the ligand T weakens the
bond trans to itself in the ground state of the complex: bond lengths,
stretching frequencies, and metal-to-ligand NMR coupling constants

The transition state effect correlates with the π " -acceptor ability of the
ligand. Its origin is thought to be the increase in electron density on the
metal atom arising due to the incoming ligand
 Coordination Chemistry
Ligand substitution in square-planar complexes
The Trans Effect
The trans effect is the combination of both effects, trans influence and
transition state effect

For a T σ-donor: OH- < NH3 < Cl- < Br- < CN-, CH3- < I- < SCN- < PR3, H-
For a T π-acceptor: Br- < I- < NCS- < NO2- < CN- < CO, C2H4

The effect of the trans

ligand in reactions of
trans-[PtCl(PEt3)2L]
 Coordination Chemistry
Excercise
Use the trans effect series to suggest synthetic routes to cis- and
trans-[PtCl2(NH3)2] from [Pt(NH3)4]2+ and [PtCl4]2-
 Coordination Chemistry
Excercise
Use the trans effect series to suggest synthetic routes to cis- and
trans-[PtCl2(NH3)2] from [Pt(NH3)4]2+ and [PtCl4]2-

Because the trans effect of Cl is greater than that of NH3, substitution

reactions will occur preferentially trans to Cl, and further action of HCl
gives trans-[PtCl2(NH3)2]

2+ + NH3
NH3 NH3
HCl HCl Cl Pt Cl
H 3N Pt NH3 H 3N Pt Cl

NH3 NH3 NH3

A second step should substitute one of the two mutually trans Cl

ligands with NH3 to give cis-[PtCl2(NH3)2]
2- NH3 - NH3
Cl
NH3 NH3
Cl Pt Cl Cl Pt Cl Cl Pt NH3

Cl Cl Cl
 Coordination Chemistry
Ligand substitution in square-planar complexes
Steric Effects
Steric crowding at the reaction centre usually inhibits associative
reactions and facilitates dissociative reactions

The rate constants for the replacement of Cl by H2O in cis-[PtClL(PEt3)2]

complexes at 25 ºC illustrate the point:

Decreasing of the rate

 Coordination Chemistry
Ligand substitution in square-planar complexes
Steric Effects
Steric crowding at the reaction centre usually inhibits associative
reactions and facilitates dissociative reactions

The rate constants for the replacement of Cl by H2O in cis-[PtClL(PEt3)2]

complexes at 25 ºC illustrate the point:

In the 2-methylpyridine complex

they block positions either above or
below the plane, however

In the 2,6-dimethylpyridine complex

they block positions both above and
below the plane
 Coordination Chemistry
Ligand substitution in square-planar complexes
Steric Effets
Steric crowding at the reaction centre usually inhibits associative
reactions and facilitates dissociative reactions

The rate constants for the replacement of Cl by H2O in cis-[PtClL(PEt3)2]

complexes at 25 ºC illustrate the point:

The effect is smaller if L is trans to Cl-.

This difference is explained by the methyl
groups then being further from the entering
and leaving groups in the trigonal-bipyramidal
transition state if the pyridine ligand is in the
trigonal plane

The decrease in coordination number that

occurs in a dissociative reaction
 Coordination Chemistry
Ligand substitution in square-planar complexes
Stereochemistry
Substitution of a square-planar complex preserves the original geometry,
which suggests a trigonal-pyramidal transition state

A cis complex gives a cis product and a trans complex gives a trans
product

Trigonal-bipyramidal intermediates of
this type account for the relatively
small influence that the two cis
spectator ligands have on the rate of
substitution

Transition state
 Coordination Chemistry
Ligand substitution in square-planar complexes
Stereochemistry
We can expect a cis ligand to exchange places with the T ligand in the
trigonal plane only if the intermediate lives long enough to be
stereomobile

The normal path is from (a) to (c). However, if intermediate (b) is sufficiently
long-lived, it can undergo pseudorotation to (d), which leads to isomer (e)
 Coordination Chemistry
Ligand substitution in square-planar complexes
Temperature and pressure dependence
Negative volumes and entropies of activation support the view that the
rate-determining step of square-planar Pt(II) complexes is associative

"ΔS‡ is obtained from the temperature dependence of the rate constant

The volume of activation is obtained from the pressure dependence of
the rate constant

Activation parameters for substitution in square-planar complexes (in methanol)