Chapter

Stability of Metal Complexes

Senthilkumar Muthaiah, Anita Bhatia
and Muthukumar Kannan

Abstract

The stability of coordination complex is an important factor that decides the

stability and reactivity of a metal complex. The stability of metal complex is
governed by two different aspects such as thermodynamic and kinetic stabilities.
The correlation between stability and reactivity of coordination compounds has
been described in this chapter. This chapter also enlists the factors influencing the
stability of metal complexes such as the nature of metal ions, ligands, bonding
between metal ions and ligands, etc. In addition, the methods available for the
determination of stability constants are given in detail.

Keywords: stability, reactivity, coordination complexes, stability constants

1. Introduction

The stability of metal complex generally means that it exists under favorable con-
ditions without undergoing decomposition and has a considerable shelf life period [1].
The term stability of metal complex cannot be generalized since the complex may be
stable to one reagent/condition and may decompose in presence of another reagent/
condition. The stability of metal complexes can be explained with the help of two
different aspects, namely, thermodynamic stability and kinetic stability [2]. Neverthe-
less, a metal complex is said to be stable if it does not react with water, which would
lead to a decrease in the free energy of the system, i.e., thermodynamic stability. On the
other hand, the complex is said to possess kinetic stability if it reacts with water to form
a stable product and there is a known mechanism through which the reaction can
proceed. For example, the system may not have sufficient energy available to break a
strong bond, although once the existing bond is broken it could be replaced by new
bond which is stronger than the older one [1]. Stability of complex compound is
assigned to be its existence in aqueous solution with respect to its bond dissociation
energy, Gibbs free energy, standard electrode potential, pH of the solution, and rate
constant or activation energy for substitution reactions.

1.1 Thermodynamic stability

Thermodynamic stability of a complex refers to its tendency to exist under

equilibrium conditions. It determines the extent to which the complex will be
formed or be converted into another complex at the point of equilibrium. In other
words, thermodynamic stability of complexes is the measure of tendency of a metal
ion to selectively form a specific metal complex and is directly related to the
metal-ligand bond energies. The thermodynamic stability of complexes is

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represented by formation constant. The formation constant is also known as stabil-

ity constant, which is the equilibrium constant obtained for the formation metal
complex [1, 2].
In general, the metal complexes are not prepared from their corresponding
starting materials in gaseous phase but are prepared in aqueous solution. In aqueous
solution, a metal cation gets hydrated to give aqua complex of the type [M(H2O)x]n+.
When a ligand replaces water molecule from aqua complex ion, a new metal complex
is formed and equilibrium is established as shown:

ð1Þ

where x is the number of water molecules, n is the oxidation number of the

metal cation, and L is the neutral and monodentate ligand. For simplicity, the above
reaction can be written in generalized form as given:

ð2Þ

The equilibrium constant Kf of the reaction is given by:

ð3Þ

In the above equation, the concentration of water is not included. Since the
solution is dilute, the water molecules which enter the bulk solution do not have
much influence on the equilibrium constant. It is observed from Eq. (3) that the
higher the value of Kf, the greater will be the stability of the complex formed. A high
value of the equilibrium constant (Kf > 1.0) also indicates that at equilibrium the
activity of complex ML is larger than the product of activities of M and L. Thus,
large value of Kf indicates that the ligand L binds to the metal ion more strongly
than H2O and hence L is a stronger ligand than H2O. If Kf is less than 1.0, then
ligand L is weaker than H2O. Thus stability constant is used as a measure of
thermodynamic stability of the complex. With a few exceptions, the value of suc-
cessive stability constants decreases regularly from K1 to Kn, that is, K1 > K2 > K3 >
… > Kn 1 > Kn. This trend is illustrated by taking formation of [Cd(NH3)4]2+ as an
example [3, 4]:

The steady decrease in the value of stepwise formation constants from K1 to Kn is

due to:

i. Increase in the number of ligands in coordination sphere that causes to

decrease the number of H2O molecules to be replaced and thus the probability
of replacement of water molecules decreased

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ii. Electrostatic factor

iii. Steric hindrance with increase in number of ligands

iv. Statistical factors (number of replaceable positions)

However, in some cases, it is found that Kn+1 > Kn because of unusual structural
changes and changes in electronic configuration of the metal ion. The change in
electronic structure of the metal ion causes the variation in the crystal field stabili-
zation energy (CFSE). The complex with higher CFSE value will be stable, and the
equilibrium constant for that complex formation will be high. One such example is
the formation of [CdBr4]2 complex in aqueous solution. The reaction of aqua
complex [Cd(H2O)6]2+ with Br ligand exhibits four stepwise equilibrium or step-
wise formation constants K1, K2, K3, and K4. The order of stepwise formation
constants is observed as follows, K1 > K2 > K3 < K4, which is not in agreement with
the common trend of K1 > K2 > K3 > K4. Aqua complex of most of the M2+ ions
including Cd2+ are octahedral, whereas the halo complexes of Cd2+ ion are tetrahe-
dral. The reaction sequence for the formation of [CdBr4]2 is given as follows:

In the final step, there is an unusual structural change from six coordinated
octahedral [Cd(H2O)3Br3] complex to four coordinated tetrahedral [CdBr4]2
complex in addition to change in the electronic configuration which lead to K4 > K3.
The formation constant (Kf) is related to the standard Gibbs free energy change
(∆G°) and standard electrode potential (E°) according to following equations:

∆G° ¼ RTlnKf (4)

∆G° ¼ nFE° (5)

hence RTlnKf ¼ nFE° (6)

Since ∆G° is a thermodynamic property, the formation constant is the measure

of thermodynamic stability. From Eqs. (4) to (6), it can be interpreted that the
thermodynamic stability of a complex can be measured in terms of formation
constant, Gibbs free energy change, and standard electrode potential. A high
negative value of ∆G° indicates that the position of equilibrium favors the product
(complex); hence the complex formed will be more stable.

1.2 Stepwise formation of complex and stepwise formation constants

The formation constant describes the formation of a complex from metal cation
and ligands. Bjerrum (1941) defined that the formation of a metal complex in
aqueous solution takes place by replacing the water molecule by another ligand (L)

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[5, 6]. It is assumed that this reaction does not occur in a single step but occurs in
several steps, and each step is characterized by its individual equilibrium constant
called as stepwise formation constant (K). For example, consider the formation of a
complex [MLn] formed by the following reactions:

By assuming the value of activity coefficients as unity, the equilibrium constant

K1 for the complex (ML) having one ligand (L) will be given as

When the metal complex ML reacts with one more ligand L,

and the equilibrium constant K2 will be

Similarly, for the formation of the complex MLn from MLn 1 and L, the equilib-
rium constant is represented as follows,

The equilibrium constants K1, K2, … , Kn are known as stepwise formation

constants. On the other hand, the equilibrium constant for the overall reaction may
be considered as

where β1, β2, β3, … , βn are the equilibrium constants called as overall
formation constants and K1, K2, K3, … , Kn are stepwise stability or formation
constants. The products of stepwise constants are Ks and βs are related one
another. For example, consider the product of stepwise formation constants
K1, K2, K3, … , Kn.

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Above equation indicates that the overall formation constant (β) is equal to the
product of the stepwise formation constant K1, K2, K3, … , Kn.

1.3 Kinetic stability

Kinetic stability is related to the reactivity of the metal complexes in solution

and deals with the rate of the reaction, its activation energy, etc. Kinetic stability is
also related to how fast a compound reacts rather than how stable it is. It aids in
determining the rate at which the reaction occurs to establish the equilibrium [7].
The term kinetic stability of complexes is classified into labile and inert by Taube
on the basis of rate of the reactions. When the rate of substitution of ligands is high,
the complex is said to be labile. For example, the copper complex of the formula
[Cu(NH3)4(H2O)2]2+ is labile. In aqueous solution the complex is blue in color, and
when concentrated hydrochloric acid is added to this solution, the solution turns
green giving rise to complex [CuCl4]2+. On the other hand, in inert complexes the
rate of ligand exchange is very slow, and the ligands are very exchanged with
difficulty. For example, the cobalt complex [Co(NH3)6]3+ reacts slowly, and no
reaction takes place at room temperature when conc. HCl was added to the aqueous
solution. However, only one NH3 ligand was found to be substituted by Cl ligand,
when the aqueous solution of the complex was heated with 6M hydrochloric acid.

2. Relation between thermodynamic and kinetic stabilities

For metal complexes, the stability and reactivity are described in thermody-
namic and kinetic terms, respectively. In particular, the terms stable and unstable
are related to thermodynamic aspects, whereas labile and inert terms are related to
kinetic aspects. As a rule of thumb, a metal complex is said to be labile if it reacts
within 1 min at 25°C, and if it takes longer time, it is considered to be inert.
Thermodynamic stability refers to the energy change that occurs while starting
materials are converted to products, that is, ∆G, for the reaction. The change in free
energy is given by the equation ∆G = ∆H T∆S = RTlnK, where ∆S is the entropy,
∆H is the enthalpy, and K is the equilibrium constant for the reaction. Kinetic
stability refers to reactivity or the ability of the metal complex to undergo ligand
substitution reactions. Complexes which undergo extremely rapid ligand substitu-
tion reaction are referred to as labile complexes, and complexes that undergo
extremely slow ligand substitution reaction are referred to as inert complexes.
Sometimes the thermodynamic and kinetic stabilities of complexes are parallel to
one another, but often they do not. One of the suitable examples for thermody-
namically stable and kinetically inert complex is [Ni(CN)4]2 as it undergoes ligand
substitution reaction very rapidly. On the other hand, the cobalt complex
[Co(NH3)6]3+ is thermodynamically unstable but kinetically inert. The complex
[Co(NH3)6]3+ is thermodynamically unstable since the complex was observed to
decompose very rapidly with rate in the order of 1025 in acidic solution. However,
no ligand substitution reaction is found when the complex is kept in acidic solution
for several days; hence the complex is kinetically inert. From the above two exam-
ples, it can be interpreted that the stability of a complex mainly depends upon the

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conditions, and it is always recommended to specify the conditions such as pH,

temperature, etc. while mentioning the stability of the complex. In brief, it is not
necessary for a stable complex to be inert and an unstable complex to be labile.
Consider the three complexes [Ni(CN)4]2 , [Mn(CN)6]3 , and [Cr(CN)6]3 .
All the complexes are thermodynamically stable, but kinetically they behave in a
different manner. The rate of exchange can be measured when carbon-14-labelled
cyanide ions are reacted with metal complexes in solution. It indicates that
[Ni(CN)4]2 is labile, [Mn(CN)6]3 is less labile, and [Cr(CN)6]3 is inert and
proves that not all stable complexes are inert and vice versa.

3. Factors affecting the stability of metal complexes

There are several factors that can affect the stability of the metal complexes
[2, 5, 8, 9], which include:

1. Nature of the central metal ion

2. Nature of the ligand

3. Chelating effect

4. Macrocyclic effect

5. Resonance effect

6. Steric effect or steric hindrance

3.1 Nature of central metal ion

3.1.1 Charge on metal cation

In metal cations, higher oxidation state forms more stable complex than lower
oxidation states with ligands such as NH3, H2O, etc. Even few exceptions are there
like CO, PMe3, o-phenanthroline, bipyridyl, CN , which form more stable complex
with lower oxidation state metals.

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3.1.2 Size of central metal cation

The stability of metal complex increases with decrease in size of the metal
cations. For M2+ ions, the general trend in stability for complexes is

Ba2þ < Sr2þ < Ca2þ < Mg2þ < Mn2þ < Fe2þ < Co2þ < Ni2þ < Cu2þ > Zn2þ

This trend in stability is known as Irving-Williams series.

This order of stability is also in good agreement with the charge to radius ratio
concept because the radii decrease from Ba2+ to Cu2+ and then increased to Zn2+.
The order of size of dipositive ions is

Ba2þ > Sr2þ > Ca2þ > Mg2þ > Mn2þ > Fe2þ > Co2þ > Ni2þ > Cu2þ < Zn2þ

3.2 Nature of ligands

Basic character of ligands: The greater is the basic character of ligand, the more
easily it can donate its lone pair of electrons to the central metal ion and hence
greater is the complex stability. In 3D-series metal ion, order of stability of complex
with NH3, H2O, and F is:

NH3 > H2 O > F

The nature of metal-ligand bond also affects the stability of metal complexes.
The higher the covalent character, the greater will be the complex stability. For
example, the stabilities of silver complexes have different halide ligands which are
in the following order:

AgI2 > AgBr2 > AgCl2 > AgF2

Ligands having vacant p- or d-orbital tend to form π bond and hence form stable
complexes with metals. Ligands that are capable of forming such π bond are CO,
CN , alkene, phenanthroline, etc.

3.3 The chelate effect

The chelate effect is that the complexes resulting from coordination of metal
ions with the chelating ligand are thermodynamically much more stable than the
complexes with non-chelating ligands [10, 11]. Chelating ligands are molecules
which can bind to single metal ion through several bonds and are also called as
multidentate ligands. Simple (and common) examples include ethylenediamine
and oxalate. Non-chelating ligands are ligands that bond to just one site, such as
chloride, cyanide, and water.
The chelate effect can be understood by comparing the reaction of a metal ion,
respectively, with a chelating ligand and with a monodentate ligand having
similar/comparable donating groups. During the comparison study, the number of
coordination should be maintained equal in both the cases, for example, the value
obtained while adding a bidentate ligand is compared with the value obtained for
two monodentate ligands. For example, coordination of metal ion with chelating
ligand 2,20 -bipyridine can be compared with that of monodentate pyridine ligand.
Another such comparison can be made between coordination behavior of chelating
1,2-diaminoethane (ethylenediamine = en) and monodentate ammonia. Such

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comparison studies revealed that the metal complex formed from chelating ligands
are thermodynamically more stable than the complex formed from monodentate
ligand. For example, formation of complexes from hydrated cadmium ion,
[Cd(H2O)4]2+ with methylamine (CH3NH2), ethylenediamine (en) and triethyle-
netetramine (trien), and their stability is in the following order:
2þ
< ½Cdðenފ2þ < ½Cdðtrienފ2þ

CdðCH3 NH2 Þ4

3.4 Macrocyclic effect

A macrocyclic ligand is a cyclic molecule that contains nine or more atoms in

the cyclic structure and has three or more potential donor atoms which can
coordinate to the metal ion. It has been observed that the stability of metal
complexes in the presence of macrocyclic ligand of appropriate size is higher
than the stability of complexes coordinated to open-ended multidentate chelating
ligands. Some notable examples of macrocyclic ligands include cyclic crown
polyether, heme, etc. [12].

3.5 Resonance effect

Resonance increases the stability of the complexes. For example, acetylacetonate

anion ligand shows resonance, and as a result it forms stable complexes upon
reacting with metal ion (Figure 1). The ligand-metal π bonding increases the
delocalization of electrons compared to free enolate as shown below and leads to
increased stability (Figure 2).

Figure 1.
Resonance structure of acetonylacetonate ligand.

Figure 2.
Acetonylacetonate-metal complex.

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3.6 Steric effect

The presence of bulky substituents in the ligands can affect the stability of the
metal complex, and this type of destabilization of metal complex due to bulkiness of
the substituent is called as steric effect [13]. For example, consider the ligand
8-hydroxy quinoline and its methyl substituted derivative 2-methyl-8-hydroxy
quinolone. Both are bidentate ligands and form chelated complexes with Ni2+ ion as
shown in Figure 3.

Figure 3.
Chelating complexes of Ni(II) ion showing steric effect.

The complex (II) is less stable than complex (I) because of bulky group attached
to an atom adjacent to donor atom which cause a steric hindrance and lower the
stability of the complex.

3.7 Crystal field stabilization energy (CFSE)

The crystal field stabilization energy (CFSE) is one of the most important factors
that decides the stability of the metal complexes. CFSE is the stability that arises when
a metal ion coordinates to a set of ligands, which is due to the generation of a crystal
field by the ligands. Thus, a higher value of CFSE means that the complex is thermo-
dynamically stable and kinetically inert. Some of the notable examples of complexes
that have high CFSE are low spin 5d6 complexes of Pt4+ and Ir3+ and square planar 5d8
complexes of Pt2+. All these complexes are thermodynamically stable and kinetically
inert, which undergo ligand substitution reactions extremely slowly [3, 4].

4. Determination of stability constants

The determination of metal complexes involves several methods including spec-

troscopic and potentiometric methods. The determination of stability constant is very
significant to understand the role and behavior of ligand(s) in stabilizing the metal
complexes and found applications in the fields of biology, environmental study,
metallurgy, food chemistry, and many other industrial processes. Some of the
methods that are used for the determination of stability constants are given as follows.

4.1 Spectroscopic methods

UV-Vis spectroscopic technique has been used to determine the stability

constant and composition of a complex [14]. The formation of metal complex is
indicated by the change in absorbance in the UV-Vis spectroscopy. The relationship
between absorbance (A) and concentration is given by Beer’s law as shown.

A ¼ ԑ:c:l: