Chapter 24: Transition elements

no double bond exists. In this case, the term geometric

isomerism refers to complexes with the same molecular
formula but different geometrical arrangements of their
atoms. Examples are cis- and trans-platin (Figure 24.8).
In cis-platin, the chlorine atoms are next to each other
in the square complex but in trans-platin, they are
opposite. The properties of these geometrical isomers
are slightly different.
CI NH3 Cl NH3

Pt Pt

CI NH3 H3N Cl
cis-platin trans-platin

Figure 24.8  The geometrical isomers, cis-platin and

trans-platin.

Cis-platin has been used as an anti-cancer drug. It acts by

Stereoisomerism in transition metal
complexes
In AS Level we learnt about two
types of stereoisomerism: geometric isomerism and
optical isomerism. The presence of a double bond in
1,2-dibromoethane means that two geometrical isomers
(cis-trans isomers) are possible. Geometric isomerism
is also possible in transition metal complexes, where
binding to sections of the DNA in cancer cells, preventing
cell division.
Stereoisomerism is commonly shown by octahedral
(six co-ordinate) complexes associated with bidentate
ligands. An example is the complex containing
nickel as the transition metal and 1,2-diaminoethane
(NH2CH2CH2NH2) as the bidentate ligand (Figure 373
24.9). The two isomers are stereoisomers because the two
different molecules are mirror images of each other and
cannot be superimposed.

a 2+ 2+
CH2 CH2
H2C NH2 H2N CH2

H2N NH2 H2N NH2

CH2 H2C
Ni Ni
CH2 H2C
H2N NH2 H2N NH2

H2C NH2 H2N CH2

CH2 CH2

b 2+ 2+
en en

Ni en en Ni

en en

Figure 24.9  The two non-superimposable optical isomers of Ni(NH2CH2CH2NH2)32+: a  the full structure; b  a simplified structure
with ‘en’ representing a molecule of 1,2-diaminoethane.
 Cambridge International A Level Chemistry

Two water ligands are replaced by two hydroxide ligands

Quest on
in the reaction:
5 a Cobalt forms a complex with the simplified
structure: [Cu(H2O)6]2+(aq)  +  2OH–(aq)
blue solution

NH2 Cu(OH)2(H2O)4(s)  +  2H2O(l)

pale blue precipitate
H2N CI
If you now add concentrated ammonia solution, the pale
CO blue precipitate dissolves and we get a deep blue solution:
H2N CI Cu(OH)2(H2O)4(s)  +  4NH3(aq)
NH2 [Cu(H2O)2(NH3) 4]2+(aq)  +  2H2O(l)   +  2OH–(aq)
the curve represents CH2 CH2 deep blue solution

The first reaction can also be achieved by adding

i Give the co-ordination number in this complex.
ii Draw the stereoisomer of this complex.
iii Explain why this is a stereoisomer.
b Draw the two geometrical isomers of Ni(CN)2(Cl)22–.
Label the cis-isomer and the trans-isomer.
Substitution of ligands
The ligands in a complex can be exchanged, wholly or
partially, for other ligands. This is a type of substitution
374
reaction. It happens if the new complex formed is
more stable than the original complex. The complexes
of copper(II) ions can be used to show ligand
substitution reactions.
Whenever we write Cu2+(aq) we are really referring to
the complex ion [Cu(H2O)6]2+. This ion gives a solution
of copper sulfate its blue colour. On adding sodium
hydroxide solution, we see a light blue precipitate forming.
concentrated ammonia solution to copper sulfate solution
drop by drop or by adding a dilute solution of ammonia.
The pale blue precipitate formed will then dissolve and
form the deep blue solution when excess ammonia is
added. The structure of [Cu(H2O)2(NH3)4]2+(aq) is shown
in Figure 24.10.
2+
H2O
H3N NH3
Cu
H3N NH3
H 2O
Figure 24.10  The structure of [Cu(H2O)2(NH3)4]2+(aq).
Water ligands in [Cu(H2O)6]2+ can also be exchanged for
chloride ligands if we add concentrated hydrochloric acid
drop by drop. A yellow solution forms, containing the
complex ion [CuCl4]2– (Figure 24.11):

start here

[CuCl4]2− [Cu(H2O)6]2+ [Cu(H2O)2(NH3)4]2+

this yellow complex forms the well-known blue Cu2+ this dark blue complex forms
on adding concentrated HCl complex with water on adding concentrated NH3

Figure 24.11  The equations for the changes are:

[Cu(H2O)6]2+  +  4Cl– [CuCl4]2–  +  6H2O and [Cu(H2O)6]2+  +  4NH3 [Cu(H2O)2(NH3)4]2+  +  4H2O.

[Cu(H2O)6]2+(aq)  +  4Cl–(aq)
blue solution
[CuCl4]2–(aq)  +  6H2O(l)
yellow solution
Aqueous cobalt(II) compounds also form complex ions.
Whenever we write Co2+(aq), we are referring to the
complex ion [Co(H2O)6]2+. This ion gives an aqueous
solution of cobalt(II) sulfate its pink colour. On adding
sodium hydroxide solution, we see a blue precipitate of
cobalt(II) hydroxide forming, which turns red when
warmed if the alkali is in excess. Water ligands in
[Co(H2O)6]2+ can also be exchanged for ammonia ligands
if we add concentrated aqueous ammonia drop by drop.
[Co(H2O)6]2+(aq)  +  6NH3(aq)
[Co(NH3)6]2+(aq)  +  6H2O(l)
The addition of concentrated hydrochloric acid drop by
drop to an aqueous solution of cobalt(II) ions results in
the formation of a blue solution containing the tetrahedral
complex [CoCl4]2–(aq).
[Co(H2O)6]2+(aq)  +  4Cl–(aq)
[CoCl4]2–(aq)  +  6H2O(l)
Aqueous cobalt(II) ions usually form tetrahedral
complexes with monodentate anionic ligands such as Cl–,
SCN– and OH–.
Quest on
6 a Blue cobalt chloride paper gets its blue colour
from [CoCl4]2– ions. What is the oxidation number
of the cobalt in this complex ion?
b Blue cobalt chloride paper is used to test for
water. If water is present the paper turns pink as
a complex forms between the cobalt ion and six
water ligands (Figure 24.12). Write an equation to
show the ligand substitution reaction that takes
place in a positive test for water.
Figure 24.12  A positive test for the presence of water
using anhydrous cobalt chloride paper.
Chapter 24: Transition elements
Stability constants
Aqueous solutions of transition element ions are hydrated.
They are complex ions with water as a ligand. Different
ligands form complexes with different stabilities. For
example when we add concentrated aqueous ammonia to
an aqueous solution of copper(II) sulfate, the ammonia
ligands displace water ligands in a stepwise process.
[Cu(H2O)6]2+ (aq)  +  NH3(aq)
[Cu(NH3)(H2O)5]2+(aq)  +  H2O(l)
[Cu(NH3)(H2O)5]2+(aq)  +  NH3(aq)
[Cu(NH3)2(H2O)4]2+(aq)  +  H2O(l)
As we increase the concentration of ammonia, this
process continues until four of the water molecules are
replaced by ammonia to form a deep blue solution. The
overall process is:
[Cu(H2O)6]2+  +  4NH3(aq)
[Cu(NH3)4(H2O)2]2+(aq)  +  4H2O(l)
We can think of this exchange of ligands in terms of
competing equilibria of the forward and backward
reactions. The position of equilibrium lies in the direction 375
of the more stable complex. In this case, the complex with
ammonia as a ligand is more stable than the complex with
just water as a ligand. If we dilute the complex with water,
the position of equilibrium shifts to the left and a complex
with more water molecules as ligands is formed.
The stability of the complex is expressed in terms of
the equilibrium constants for ligand displacement. This is
called the stability constant. Usually an overall stability
constant, Kstab, is given rather than the stepwise constants.
The stability constant is the equilibrium constant for the
formation of the complex ion in a solvent from its constituent
ions or molecules. The method for writing equilibrium
expressions for stability constants is similar to the one we
used for writing Kc . So for the equilibrium
[Cu(H2O)6]2+  +  4Cl–(aq) [CuCl4]2–(aq)  +  6H2O(l)
the expression is:
[[CuCl4]2–(aq)]
Kstab =_____________________
​ 
    ​
[[Cu(H2O)6]2+] [Cl–(aq)]4
Note:
■■ water does not appear in the equilibrium expression
because it is in such a large excess that its concentration is
regarded as being constant
 Cambridge International A Level Chemistry

■■ the units for the stability constant are worked out in the
Quest on
same way as for the units of Kc . For example, in the above
case: 7 a Write expressions for the stability constants for the
[[CuCl4]2–(aq)] (mol dm–3) following reactions:
Kstab = _____________________
​   
    ​ _____________________
  
​     ​
[[Cu(H2O)6]2+] [Cl–(aq)]4 –3 –3 4
(mol dm ) × (mol dm ) i [PtCl4]2–(aq)  +  2NH3(aq)

= dm12 mol–4 PtCl2(NH3)2(aq)  +  2Cl–(aq)

ii [Cr(H2O)6]3+(aq)  +  2Cl–(aq)
Stability constants are often given on a log10 scale. When
[Cr(H2O)4Cl2]+(aq)  +  2H2O(l)
expressed on a log10 scale, they have no units. Stability
constants can be used to compare the stability of any two iii [Ni(H2O)6]2+(aq)  +  4NH3(aq)
ligands. The values quoted usually give the stability of the [Ni(NH3)4(H2O)2]2+(aq)  +  4H2O(l)
complex relative to the aqueous ion where the ligand is b An iron(III) ion, Fe3+, in aqueous solution has six
water. The higher the value of the stability constant, the water molecules bonded to it as ligands.
more stable the complex. Table 24.5 gives some values i Draw the structure of this ion.
of stability constants for various copper(II) complexes
ii When thiocyanate ions, SCN–, are added to
relative to their aqueous ions. an aqueous solution of iron(III) ions, the
solution turns red and one water molecule is
Ligand log10 Kstab replaced by a thiocyanate ion. Use the concept
chloride, Cl–  5.6 of stability constants to explain why the
reaction occurs.
ammonia, NH3 13.1
iii Deduce the formula of the ion forming the
2-hydroxybenzoate 16.9 red solution.
CO2–
iv The stability constant for aqueous Fe3+ ions
376 OH with SCN– as a ligand is 891 dm3 mol–1. The
stability constant for aqueous Fe3+ ions with
1,2-dihydroxybenzene OH 25.0 fluoride ions, F–, as a ligand is 2 × 105 dm3 mol–1.
A solution containing fluoride ions is added to
OH the red solution. Would you expect to observe
any changes? Explain your answer.
Table 24.5  The stability constants of some complexes
of copper.

From the table you can see that, in general, complexes

with bidentate ions (2-hydroxybenzoate and
1,2-dihydroxybenzene) have higher stability constants than
those with monodentate ligands. We can use the values of
the stability constants to predict the effect of adding different
ligands to complex ions. For example, the addition of excess
ammonia to the complex [CuCl4]2–(aq) should result in the
formation of a dark blue solution of the ammonia complex
because the stability constant of the ammonia complex is
higher than that of the chloride complex. The position of
equilibrium is shifted to the right in the direction of the more
stable complex. Addition of excess 1,2-dihydroxybenzene
to the dark blue ammonia complex results in the formation
of a green complex with 1,2-dihydroxybenzene. This is
because the stability constant with the 1,2-dihydroxybenzene
is higher than that for ammonia:
OH O O 2–
2+
[Cu(NH ) ] + 2 Cu + 4H++ 4NH4+
3 4
OH O O