Subject 4

(Lecture Notes)
Outlines of lecture

Stability constants of transition metal complexes

Factor affecting stability constant

 Stability constants of complexes

A stability constant (formation constant, binding constant)
is an equilibrium constant for the formation of a complex in
solution. It is a measure of the strength of the interaction
between the metal and ligands that come together to form a
complex.
There are two main kinds of complexs, Compounds formed
by the interaction of a metal ion with a ligand and
supramolecular complexes, such as host-guest complexes and
complexes of anions.
The formation of a metal complex with a ligand was a kind of acidbase equilibrium, there is competition for the for the reaction of
ligand, L with metal ion, Mn+, and the hydrogen ion, H+. This means
that there are two simultaneous equilibria that have to be
considered.
H+L

HL

M+L

ML

The stability constant for the formation of a complex (ML)

could be determined as below:
M + nL

MLn

Stepwise formation and cumulative constants

The formation constant is the sum of stepwise constant,
given the symbol K, is the constant for the formation of a

complex from reagents. For example, the formation constant

for the formation of MLn is given by
[ML]
[M][L]
[ML2]
K2 =
[ML][L]

M+L

ML

K1=

ML + L

ML2

ML2 + L

ML3

K3 =

MLn + L

MLn+1

Kn = [MLn+1]
[MLn][L]

[ML3]
[ML2][L]

The stepwise constants, K1, K2, K3 and Kn refer to the

formation of the complexes one step at a time. The over all
formation constant is:
Kf = K1 x K2 x K3.Kn
A cumulative or overall constant, given the symbol , a
cumulative constant can always be expressed as the product
of stepwise constants.
[ML]
[M][L]
[ML2]
[M][L]2

M+L

ML

1=

M + 2L

ML2

2 =

M + 3L

ML3

3 =

[ML3]
[M][L]3

M + nL

MLn

n =

[MLn]
[M][L]n

Conversely, any stepwise constant can be expressed as a

quotient of two or more overall constants.
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1 = K1
2 = K1 x K2
2 = K1 x K2 x K3

n K 1 K 2 .......

in

Kn Ki
i 1

It is best always to define each stability constant by

reference to an equilibrium expression.

Factors affecting the stability constants of

complexes
1. The chelate effect:
An inorganic metal complex in which there is a close ring of
atoms caused by attachment of a ligand to a metal atom at
two points. An example is the complex ion formed between
ethylene diamine and cupric ion, [Cu(NH2CH2NH2)2]2+.

H2
N

H2
N
Cu2+

N
H2

N
H2

The chelate effect in action: two monodentates are replaced

by a single chelating agent, resulting in a higher K value,
increased exothermicity, and a positive entropy change.

H2N
2

H3N

NH3

H2
N
H2N

Cu2+

Cu2+
H3N

H2
N

N
H2

NH3

N
H2

Cu2+ complexes with 4 ammonia (left) and two ethylene

diamine (right) Consider the two equilibria, in aqueous
solution,

between

the

copper(II)

ion,

Cu2+

and

ethylenediamine (en) on the one hand and ammonia on the

other.
Cu2+ + 2en
Cu2+ + 4NH3

[Cu(en)2]2+ (1)
[Cu(NH3)4]2+ (2)

In (1) the bidentate ligand ethylene diamine forms a chelate

complex with the copper ion. Chelation results in the
formation of a fivemembered ring. In (2) the bidentate
ligand is replaced by 4 monodentate ammonium ligands of
approximately the same donor power, meaning that the
enthalpy of formation of CuN bonds is approximately the
same in the two reactions. Under conditions of equal copper
concentrations and when then concentration of ammonia is
twice

the

concentration

of

ethylenediamine,

the

concentration of the complex (1) will be greater than the

concentration of the complex (2).
The chelate effect increases as the number of chelate rings
increases. For example the complex [Ni(dien)2)]2+ is more
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stable than the complex [Ni(en)3)]2+; both complexes are

octahedral with six nitrogen atoms around the nickel ion, but
dien (diethylenetriamine, 1,4,7-triazaheptane) is a tridentate
ligand and en is bidentate.

H2N
H2N

NH2 H2
N
Ni2+
NH2

N
H2

NH
H2N
H2N

[Ni(en)3)]2+

Ni2+

NH2
NH2

NH

[Ni(dien)2)]2+

The effect increases with the number of chelate rings so the

concentration of the EDTA complex, which has six chelate
rings, is much higher than a corresponding complex with two
monodentate nitrogen donor ligands and four monodentate
carboxylate ligands. Thus, the phenomenon of the chelate
effect is a firmly established empirical fact: under
comparable conditions, the concentration of a chelate
complex will be higher than the concentration of an analogous
complex with monodentate ligands.

 The number of chelate rings is one less than the number of

donor atoms in the ligand. EDTA (ethylenediaminetetracetic
acid) has six donor atoms so it forms very strong complexes
with five chelate rings. Ligands such as DTPA, which have
eight donor atoms are used to form complexes with large
metal ions such as lanthanide or actinide ions which usually
form 8- or 9- coordinate complexes.
5-membered and 6-membered chelate rings give the most
stable complexes. 4-membered rings are subject to internal
strain because of the small inter-bond angle in the ring. The
chelate effect is also reduced with 7-and 8-membered rings,
because the larger rings are less rigid, so less entropy is lost
in forming them.

Ethylenediamine (en) Diethylenetriamine (dien)

Effect of donor atoms on stability constant

According to Irving-Williams series Mn < Fe < Co < Ni < Cu > Zn
for more detail go on page 13.
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2. Effect of donor atoms:

The stability constant also affected by the nature of donor
groups such as electronagetivity, radii etc. For example,
Nitrogen has smaller size than oxygen so it form more stable
complex than oxygen, on the other hand the nature of binding
on the type of the bonds such as coordination bonds (less
stable) and covalent coordination (more stable) bond as given
below:

According to Irving-Williams series Mn < Fe < Co < Ni < Cu > Zn for

more detail go on page 13.
3. The macrocyclic effect:
It was found that the stability of the complex of metals ions
with the macrocyclic ligand was much greater than expected in
comparison to the stability of the complexs with the
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corresponding open-chain. This phenomenon was named "the

macrocyclic effect" and it ares also interpreted as an entropy
effect. However, later studies suggested that both enthalpy
and entropy factors were involved.
An important difference between macrocyclic ligands and
open-chain (chelating) ligands is that they have selectivity
for metal ions, based on the size of the cavity into which the
metal ion is inserted when a complex is formed. For example,
the crown ether 18-crown-6 forms much stronger complexes
with the potassium ion, K+ than with the smaller sodium ion,
Na+.

4. The effect of metal ions

Ahrland, Chatt and Davies proposed that metal ions could be
described as class A if they formed stronger complexes with
ligands whose donor atoms are N, O or F than with ligands

whose donor atoms are P, S or Cl and class B if the reverse is

true.
For example: Ni2+ forms stronger complexes with amines
than with phosphines, but Pd2+ forms stronger complexes
with phosphines than with amines. Later, Pearson proposed
the theory of hard and soft acids and bases (HSAB theory).
Type of
Acid/Base
Hard acids

Soft acids

Border line
acids
Hard bases

Soft bases

Border line
bases

CHARACTERISTICS
* Atomic centres of small ionic radii
(<90 pm).
* High positive charge.
* Empty orbitals in their valence shells.
* Low electronegativity (0.7-1.6) and
low electron affinity.
* Likely to be strongly solvated.
* High energy LUMO.
* Large radii (>90 pm).
* Low or partial positive charge.
* Completely filled orbitals in their
valence shells.
* Intermediate electronegativities (1.92.5)
* Low energy LUMO's with large
magnitude of LUMO coefficients.

* Small radii (around 120pm) & highly

solvated .
* electronegative atomic centres (3.04.0).
* Weakly polarizable.
* Difficult to be oxidized.
* High energy HOMO.
* Large atoms (>170 pm) with
intermediate electronegativity (2.53.0).
* High polarizability
* Easily undergo oxidation.
* Low energy HOMO's but large
magnitude HOMO coefficients.

EXAMPLES
H+, Li+, Na+, K+, Be2+, Mg2+, Ca2+,
Sr2+, Sn2+
Al3+, Ga3+, In3+, Cr3+, Co3+, Fe3+,
Ir3+, La3+, Si4+, Ti4+, Zr4+, Th4+,
VO2+ , UO22+
BeMe2, BF3, BCl3, B(OR)3, AlMe3
Cu+, Ag+, Au+, Hg+ , Cs+ , Tl+ ,
Hg2+ , Pd2+, Cd2+ , Pt2+
Metal atoms in zero oxidation
states

Fe2+ , Co2+ , Ni2+ , Cu2+ , Zn2+ ,

Pb2+ , B(CH3)3, SO2, NO+
H2O, OH-, F-, Cl-, CH3CO2-, PO43, SO42-, CO32-, NO3-, ClO4-, ROH,
RO-, R2O, NH3, RNH2, N2H4

RSH, RS-, R2S, I-, CN-, SCN-,

S2O3-, R3P, R3As (RO)3P, RNC,
CO, C2H4, C6H6, R-, H-

Aniline, pyridine, N3-, Br-, NO2-,

SO32-, N2

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In this classification, class A metals are hard acids and class B

metals are soft acids. Some ions, such as copper(i) are classed
as borderline. Hard acids form stronger complexes with hard
bases than with soft bases. In general terms hard-hard
interactions are predominantly electrostatic in nature whereas
soft-soft interactions are predominantly covalent in nature. The
HSAB theory, though useful, is only semi-quantitative.
The hardness of a metal ion increases with oxidation state. An
example of this effect is given by the fact that Fe2+ tends to
form stronger complexes with N-donor ligands than with Odonor ligands, but the opposite is true for Fe3+.
5. Effect of ionic radius
The Irving-Williams series refers to high-spin, octahedral,
divalent metal ion of the first transition series. It places the
stabilities of complexes in the order
Mn < Fe < Co < Ni < Cu > Zn
This order was found to hold for a wide variety of ligands.
There are three strands to the explanation of the series.
1. The ionic radius is expected to decrease regularly for Mn2+
to Zn2+. This would be the normal periodic trend and would
account for the general increase in stability.
2. The crystal field stabilisation energy (CFSE) increases from
zero for manganese(II) to a maximum at nickel(II). This

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makes the complexes increasingly stable. CFSE returns to

zero for zinc(II).
3. Although the CFSE for copper(II) is less than for nickel(II),
octahedral copper(II) complexes are subject to the JahnTeller effect which results in a complex having extra
stability.

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Practice Problems
1. Based on the given values, rank the following complex ions
from most to least stable.
[Cr(OH)4]

Kf=8.01029

[Ni(CN)4]2

Kf=2.01031

[Co(NH3)6]3+

Kf=4.51033

[Cu(CN)4]3

Kf=2.01030

2. Of [Ni(en)3]2+, [Ni(EDTA)]2, and [Ni(NH3)6]2+ which would

you expect to have the largest kf value? The smallest?
Explain.

3.The formation of [Ni(en)3]2+ is a three step proccess with

the following stepwise formation constants K1=3.3107,
K2=1.9106, and K3=1.8104. Using this information find the
overall formation constant and the formation constant for
each of the intermediate steps.
4.Write equation for the stepwise stability constant of the
flowing reaction:
[Cu(H2O)6] + 4 NH3

[Cu(H2O)2(NH3)4] + 4H2O

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