Transition Metal Chemistry

What is a complex ion?

A complex ion has a metal ion at its centre with a number of other molecules
or ions surrounding it. These can be considered to be attached to the central
ion by co-ordinate (dative covalent) bonds. (In some cases, the bonding is
actually more complicated than that.)
The molecules or ions surrounding the central metal ion are called ligands.
Simple ligands include water, ammonia and chloride ions.
What all these have got in common is active lone pairs of electrons in the
outer energy level. These are used to form co-ordinate bonds with the metal
ion.
Some examples of complex ions formed by transition metals
[Fe(H
2
O)
6
]
2+
[Co(NH
3
)
6
]
2+
[Cr(OH)
6
]
3-
[CuCl
4
]
2-
Other metals also form complex ions - it isn't something that only transition
metals do. Transition metals do, however, form a very wide range of complex
ions.
The formation of coloured compounds
Some common examples
The diagrams show approximate colours for some common transition metal
complex ions.
You will fnd these and others discussed if you follow links to individual metals
from the transition metal menu (link at the bottom of the page).
Alternatively, you could explore the complex ions menu (follow the link in the
help box which has just disappeared of the top of the screen).
The origin of colour in the transition metal ions
When white light passes through a solution of one of these ions, or is refected
of it, some colours in the light are absorbed. The colour you see is how your
eye perceives what is left.
Attaching ligands to a metal ion has an efect on the energies of the d orbitals.
Light is absorbed as electrons move between one d orbital and another. This
is explained in detail on another page.
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
2
O)
6
]
2+
, four of the water molecules are eventually replaced by ammonia
molecules to give [Cu(NH
3
)
4
(H
2
O)
2
]
2+
.
This can be written as an equilibrium reaction to show the overall efect:
Individual stability constants
Let's take a closer look at the frst of the 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 frst water
molecule to be replaced, we call it K
1
.
K
1
is given by this expression:
There are two points of possible confusion here - one minor, one more
important!
First, the square brackets have changed their meaning! Square brackets
are often used to keep everything in a complex ion together and tidy.
Here, they have reverted to their other use, which implies
concentrations in mol dm
-3
.
In order to avoid complete confusion, the square brackets keeping the
complexes together have been removed entirely.
More importantly, if you compare the equilibrium constant expression with
the equation, you will see that the water on the right-hand side hasn't
been included. That is normal practice with these expressions.
The concentration of the water is approximately constant. The
equilibrium constant is defned so that you avoid having an extra
unnecessary constant in the expression.
Introduce a value for K
1
:
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.
Ligand exchange colour changes