Transition Metal Handout

The elements in the Periodic Table which correspond to the d levels filling are called d
block elements. The first row of these is shown in the shortened form of the Periodic
Table below.

The electronic structures of the d block elements shown are:

Sc [Ar] 3d14s2

Ti [Ar] 3d24s2

V [Ar] 3d34s2

Cr [Ar] 3d54s1

Mn [Ar] 3d54s2

Fe [Ar] 3d64s2

Co [Ar] 3d74s2

Ni [Ar] 3d84s2

Cu [Ar] 3d104s1

Zn [Ar] 3d104s2

A TRANSITION METAL IS ONE WHICH FORMS ONE OR MORE STABLE IONS

WHICH HAVE INCOMPLETELY FILLED d ORBITALS

When d-block elements form ions, the 4s electrons are lost first. To write the electronic
structure for Co2+:

Co [Ar] 3d74s2

Co2+ [Ar] 3d7

The 2+ ion is formed by the loss of the two 4s electrons.

EXAMPLES OF VARIABLE OXIDATION STATES IN THE TRANSITION

METALS

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Iron has two common oxidation states (+2 and +3) in, for example, Fe2+ and Fe3+.
Manganese has a very wide range of oxidation states in its compounds. For example:

+2 in Mn2+

+3 in Mn2O3

+4 in MnO2

+6 in MnO42-

+7 in MnO4-

The diagrams show approximate colours for some common transition metal complex
ions.

THE ORIGIN OF COLOUR IN THE TRANSITION METAL IONS

When white light passes through a solution of one of these ions, or is reflected off 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 effect on the energies of the d orbitals. Light is
absorbed as electrons move between one d orbital and another.

CATALYTIC ACTIVITY

Transition metals and their compounds are often good catalysts. Transition metals and
their compounds function as catalysts either because of their ability to change
oxidation state or, in the case of the metals, to adsorb other substances on to their
surface and activate them in the process.

REDUCING VANADIUM(V) IN STAGES TO VANADIUM(II)

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The usual source of vanadium in the +5 oxidation state is ammonium metavanadate,
NH4VO3. This isn't very soluble in water and is usually first dissolved in sodium
hydroxide solution. The solution can be reduced using zinc and an acid - either
hydrochloric acid or sulphuric acid, usually using moderately concentrated acid.
The reaction is done under acidic conditions when the main ion present is VO2+ -
called the dioxovanadium(V) ion.
The reduction is shown in two stages. Some individual important colours are shown,
but the process is one continuous change from start to finish.

The reduction from +5 to +4

The reduction from +4 to +2

The colour changes just continue.

WHAT IS A COMPLEX METAL 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.

The molecules or ions surrounding the central metal ion are called LIGANDS.

The table shows some common ligands and the code for them in the name of a complex
ion.

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ligand coded by (old name)

H2O aqua aquo

NH3 ammine ammino

OH- hydroxo hydroxy

Cl- chloro  

F- fluoro  

CN- cyano  

Coding for the number of ligands

The normal prefixes apply if there is more than one ligand.

no of ligands coded by

2 di

3 tri

4 tetra

5 penta

6 hexa

Putting this together

For a complex ion containing only one type of ligand, there is no problem. For
example:[Cu(H2O)6]2+ is called the hexaaquacopper(II) ion.[Cu(NH3)4(H2O)2]2+ is
called the tetraamminediaquacopper(II) ion.The "ammine" is named before the
"aqua" because "am" comes before "aq" in the alphabet. The "tetra" and "di" are
ignored.

Naming the metal

It depends on whether the complex ion ends up as positively or negatively charged.

• For positively charged complex ions. A positively charged complex ion is called
a cationic complex. A cation is a positively charged ion.The metal in this is
named exactly as you would expect, with the addition of its oxidation state.

• For negatively charged complex ions. A negatively charged complex ion is

called an anionic complex. An anion is a negatively charged ion.In this case the
name of the metal is modified to show that it has ended up in a negative ion.
This is shown by the ending –ate

Common examples include:

metal changed to

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cobalt cobaltate

aluminium aluminate

chromium chromate

vanadium vanadate

copper cuprate

iron ferrate

SOME SIMPLE SHAPES FOR COMPLEX IONS

These shapes are for complex ions formed using monodentate ligands - ligands which
only form one bond to the central metal ion.

6-CO-ORDINATED COMPLEX IONS

These are complex ions in which the central metal ion is forming six bonds, that means
that it will be attached to six ligands. These ions have an octahedral shape. Four of the
ligands are in one plane, with the fifth one above the plane, and the sixth one below the
plane.

The diagram shows four fairly random examples of octahedral ions

4-CO-ORDINATED COMPLEX IONS

These are far less common, and they can take up one of two different shapes.
Tetrahedral ions
There are two very similar ions which crop up commonly at this level: [CuCl4]2- and
[CoCl4]2-.The copper(II) and cobalt(II) ions have four chloride ions bonded to them

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rather than six, because the chloride ions are too big to fit any more around the central
metal ion.

A SQUARE PLANAR COMPLEX

Occasionally a 4-co-ordinated complex turns out to be square planar. There's no easy
way of predicting that this is going to happen. Cisplatin is a neutral complex,
Pt(NH3)2Cl2. It is neutral because the 2+ charge of the original platinum(II) ion is
exactly cancelled by the two negative charges supplied by the chloride ions.

WHY DO WE SEE SOME COMPOUNDS AS BEING COLOURED?

White light
If you pass white light through a prism it splits into all the colours of the rainbow.
Visible light is simply a small part of an electromagnetic spectrum most of which we
can't see - gamma rays, X-rays, infra-red, radio waves and so on.

Each of these has a particular wavelength, ranging from 10-16 metres for gamma rays
to several hundred metres for radio waves. Visible light has wavelengths from about
400 to 750 nm. (1 nanometre = 10-9 metres.)

The diagram shows an approximation to the spectrum of visible light.

Why is copper(II) sulphate solution blue?

If white light (ordinary sunlight, for example) passes through copper(II) sulphate
solution, some wavelengths in the light are absorbed by the solution. Copper(II) ions in
solution absorb light in the red region of the spectrum.

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The light which passes through the solution and out the other side will have all the
colours in it except for the red. We see this mixture of wavelengths as pale blue (cyan).

The diagram gives an impression of what happens if you pass white light through
copper(II) sulphate solution.

THE ORIGIN OF COLOUR IN COMPLEX IONS CONTAINING TRANSITION

METALS
Complex ions containing transition metals are usually coloured, whereas the similar
ions from non-transition metals aren't. That suggests that the partly filled d orbitals
must be involved in generating the colour in some way.

Remember that transition metals are defined as having partly filled d orbitals.

The diagram shows the arrangement of the d electrons in a Cu2+ ion before and after
six water molecules bond with it.

Whenever 6 ligands are arranged around a transition metal ion, the d orbitals are
always split into 2 groups in this way - 2 with a higher energy than the other 3.

The size of the energy gap between them (shown by the blue arrows on the diagram)
varies with the nature of the transition metal ion, its oxidation state (whether it is 3+ or
2+, for example), and the nature of the ligands.

The diagrams show some approximate colours of some ions based on chromium(III).

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For example, a commonly quoted case comes from cobalt(II) chemistry, with the ions
[Co(H2O)6]2+ and [CoCl4]2-.

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

The colour of the tetrachlorocuprate(II) ion is almost always seen mixed with that of
the original hexaaqua ion.
What you normally see is:

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