COMPLEX METAL IONS - LIGAND EXCHANGE REACTIONS

Examples of ligand exchange reactions

A ligand exchange reaction is exactly what it says - a reaction in which one ligand in a complex ion is
replaced by a different one.

The strength of the ligands as Lewis base, varies from ligand to ligand. A ligand which is a strong Lewis
base can displace a weaker Lewis base.

 Spectrochemical series

Weak field I- < Br- < Cl- < NO3- < F- < OH- < H2O < Pyridine < NH3 < NO2- < CN- < CO Strong field

Replacing water with chloride ions

Replacing the water in the hexaaquacobalt(II) ion

If you add concentrated hydrochloric acid to a solution containing hexaaquacobalt(II) ions (for example,
cobalt(II) chloride solution), the solution turns from its original pink colour to a dark rich blue. The six
water molecules are replaced by four chloride ions.

The reaction taking place is reversible.

Concentrated hydrochloric acid is used as the source of chloride ions because it provides a very high
concentration compared to what is possible with, say, sodium chloride solution. Concentrated
hydrochloric acid has a chloride ion concentration of approximately 10 mol dm -3.

The high chloride ion concentration pushes the position of the equilibrium to the right according to Le
Chatelier's Principle.

Notice the change in the co-ordination of the cobalt. Chloride ions are bigger than water molecules, and
there isn't room to fit six of them around the central cobalt ion.

This reaction can be easily reversed by adding water to the solution. Adding water to the right-hand side
of the equilibrium has the effect of moving the position of equilibrium to the left. The pink colour of the
hexaaquacobalt(II) ion is produced again (only paler, of course, because it is more dilute).
Replacing the water in the hexaaquacopper(II) ion

In terms of the chemistry, this is exactly the same as the last example - all that differs are the colours.
Unfortunately, these aren't quite so straightforward. The colour of the tetrachlorocuprate(II) ion is
almost always seen mixed with that of the original hexaaqua ion.

What you normally see is:

The reaction taking place is reversible, and you get a mixture of colours due to both of the complex ions.

You may find the colour of the tetrachlorocuprate(II) ion variously described as olive-green or yellow.

Adding water to the green solution, replaces the chloride ions as ligands by water molecules again, and
the solution returns to blue.
Replacing the water in the hexaaquacopper(II) ion

This is a slightly untypical case, because only four of the six water molecules get replaced to give the
tetraamminediaquacopper(II) ion, [Cu(NH 3)4(H2O)2]2+.

Notice that the four ammonias all lie in one plane, with the water molecules above and below.

What you see in a test tube is:

The main equilibrium involved in the ligand exchange reaction is:

The colour of the deep blue complex is so strong that this reaction is used as a sensitive test for
copper(II) ions in solution. Even if you try to reverse the change by adding large amounts of water to the
equilibrium, the strength of the deep blue (even highly diluted) always masks the pale blue of the aqua
ion.
Replacing the water in the hexaaquacobalt(II) ion

This time, all the water molecules get replaced.

The straw coloured solution formed changes colour very rapidly on standing to a deep reddish brown.
The hexaamminecobalt(II) ions are oxidised by the air to hexaamminecobalt(III) ions. However, that is a
quite separate reaction, and isn't a part of the ligand exchange reaction.

Replacing the water in the hexaaquachromium(III) ion

Again, all the water molecules get replaced by ammonias. The difference this time is that the reaction
isn't so complete. The precipitate has to be left to stand in the presence of excess concentrated
ammonia solution for some time in order to get the ammine complex.

Even so, you still get left with some unreacted precipitate.
COMPLEX METAL IONS - STABILITY CONSTANTS

What is a stability constant?

Replacing water by ammonia around copper(II) ions

If you add ammonia solution to a solution containing hexaaquacopper(II) ions, [Cu(H 2O)6]2+, four of the
water molecules are eventually replaced by ammonia molecules to give [Cu(NH 3)4(H2O)2]2+.

This can be written as an equilibrium reaction to show the overall effect:

In fact, the water molecules get replaced one at a time, and so this is made up of a series of part-
reactions:

All that is happening is that first you have one, then two, then three, then four water molecules in total
replaced by ammonias.

Individual stability constants

Let's take a closer look at the first of these equilibria:

Like any other equilibrium, this one has an equilibrium constant, K c - except that in this case, we call it
a stability constant. Because this is the first water molecule to be replaced, we call it K 1.

Here is the equation again:

K1 is given by this expression:

The value of the equilibrium constant is fairly large, suggesting that there is a strong tendency to form
the ion containing an ammonia molecule.

A high value of a stability constant shows that the ion is easily formed.

Each of the other equilibria above also has its own stability constant, K 2, K3 and K4. For example, K2 is
given by:

The ion with two ammonias is even more stable than the ion with one ammonia.

You could keep plugging away at this and come up with the following table of stability constants:

ion Kn value (mol-1 dm3) log Kn

[Cu(NH3)(H2O)5]2+ K1 1.78 x 104 4.25

[Cu(NH3)2(H2O)4]2+ K2 4.07 x 103 3.61

[Cu(NH3)3(H2O)3]2+ K3 9.55 x 102 2.98

[Cu(NH3)4(H2O)2]2+ K4 1.74 x 102 2.24

The ions keep on getting more stable as you replace up to 4 water molecules, but notice that the
equilibrium constants are gradually getting less big as you replace more and more waters. This is
common with individual stability constants.

Overall stability constants

The overall stability constant is simply the equilibrium constant for the total reaction:

It is given by this expression:

You can see that overall this is a very large equilibrium constant, implying a high tendency for the
ammonias to replace the waters. The "log" value is 13.1.

This overall value is found by multiplying together all the individual values of K 1, K2 and so on.

Summary

Whether you are looking at the replacement of individual water molecules or an overall reaction
producing the final complex ion, a stability constant is simply the equilibrium constant for the reaction
you are looking at.

The larger the value of the stability constant, the further the reaction lies to the right. That implies that
complex ions with large stability constants are more stable than ones with smaller ones.

Stability constants tend to be very large numbers. In order to simplify the numbers a "log" scale is often
used. 
Ligand substitution and stability constants

Haemoglobin and ligand substitution

Haemoglobin - is made from 2 parts
a)  Haem:                                                                                            b)  Globin:

 Haem is a non
protein
molecule  Globin is made
complex that from 4
can bind to proteins joined
Fe2+ ions. together in a
 It forms 4 polypeptide.
dative covalent  They are
bonds to Fe2+. optical isomers
 Its coordination of each other.
number is 4 and  Each protein
binds in a forms a dative
square planar covalent bond
arrangement. to the Fe2+
 This allows 2  This leaves 1
further dative area free for a
covalent bonds dative covalent
- 1 above and 1 bond.
below.

 
The water molecule which is bonded to the bottom position in the diagram is easily replaced by an
oxygen molecule (again via a lone pair on one of the oxygens in O 2) - and this is how oxygen gets carried
around the blood by the haemoglobin.

When the oxygen gets to where it is needed, it breaks away from the haemoglobin which returns to the
lungs to get some more.

A simpler picture:

 Looking at one of the haem complexes which forms a further dative covalent bond with one of
the proteins in globin.

 A space is left for a further dative covalent bond.  This is where oxygen forms a dative covalent
bond in order to be transported around the body.

 It also forms a complex with carbon dioxide which is transported back to the lungs.

Carbon monoxide - the silent killer

 Carbon monoxide can bind to haemoglobin sites in exactly the same way as oxygen.

 Carbon monoxide however binds more favourable than oxygen.

 This results in the tissues being starved of oxygen.

 To make matters worse - once carbon monoxide binds to the haem site, it cannot be removed.

 That haem site is now useless.

 The complex ion formed is much more stable with carbon monoxide than with oxygen.

 This reaction is a simple ligand substitution reaction.

Cyanide would have this effect also.