Transition Metals part 1

General
By now you should know where the transition metals are in the periodic table. They are sometimes
referred to as the d-block elements in reference to their d orbitals.

Transition metals are used: as catalysts e.g. Ni in the Haber Process

as reducing agents e.g. Zn

as complex ions (mostly coloured)

and as oxidising agents e.g. MnO4-.

Transition metal definition: a metal that can form one or more ions that have partially filled d orbitals.

Zn and Sc are the exceptions: they have filled and empty shells for the Zn 2+ and Sc3+ ions (not partially
filled), and are therefore NOT transition metals (see further down for more detail).

Physical properties transition metals have similar physical properties e.g. high density, high boiling or
melting point and similar ionic radii.

Variable oxidation states: used in catalysis.

Oxidation states
Most transition metals have variable oxidation states. Why do they form different oxidation states? As
with most things chemistry related, it is all stability related. If the ions are stable enough, then they will
form!

you dont have to remember every transition metal and all their oxidation states but it is useful to
have a rough idea of what metals form what ions.

Electronic Configuration
When talking about transition metals, we are looking at the d subshell (3d for the first period, 4d for the
second period and 5d for the third period).

There are five orbitals in every d sub-shell. Therefore, you can have 10 electrons in a d sub-shell
(remember that you can only put 2 electrons in each individual orbital).

The orbital order is: 1s 2s 2p 3s 3p 4s 3d

The 4s orbital comes BEFORE the 3d orbitals i.e. the 4s orbital is at lower energy than 3d.

The easiest way to deal with this is to accept it. There are many complicated explanations and
assumptions regarding this, which you dont need to worry about.
 you might see some books or notes where they write out an electronic configuration with 3d before
4s. I dont know why they do this but stick to 4s before 3d as it is always correct.

Example

Mn has 25 electrons in total so write out the electronic configuration first:

1s2 2s2 2p6 3s2 3p6 4s2 3d5

Then fill up the orbitals as you did at AS level i.e. one electron in each 3d orbital (the inner orbitals 1s to
3p are not included in the diagram):

Transition Metal Ions

remove electrons from the 4s orbital before the 3d

Example

Mn: 1s2 2s2 2p6 3s2 3p6 4s2 3d5 to Mn2+: 1s2 2s2 2p6 3s2 3p6 3d5

I know that it makes sense to think that youd remove them from the 3d first, as it was filled last, but no!
Again, it is best just to accept this.

Exceptions
Zn and Sc
We mentioned that Zn and Sc are not transition metals earlier.

You need to remember that the definition refers to their ions and not the metals themselves.

The ions that they form are Zn2+ and Sc3+, which means that Zn2+ has a full 3d shell i.e. 3d10 and Sc3+ has
an empty 3d shell i.e. 3d0. Therefore, they are not transition metals but are still in the d-block.
Cu and Cr

For stability reasons Cu and Cr exist as: Cu 4s1 3d10 and Cr 4s1 3d5

Youd probably expect 4s2 3d9 and 4s2 3d4 from our theory above.

Again, you dont really need to know the complicated reasons behind this other than that they are just
more stable having half filled 3d orbitals for Cr and full 3d orbitals for Cu.

Cu+ is unusual but it does exist. If you do see Cu+, then you need to immediately start thinking of
disproportionation i.e. when something is BOTH oxidised and reduced at the same time:

2Cu+ Cu + Cu2+

Complex Ions
A complex ion consists of a central metal ion surrounded by ligands.

A ligand is a molecule that has at least one lone pair of electrons.

NH3, H2O, CN-, Cl- are very common ligands and are used all the time in questions

NH3 and H2O are neutral species (as they only have a lone pair), whereas CN- and Cl- have a 1- charge.

Formation

A ligand donates a pair of electrons to the metal to form a dative covalent bond, also known as a
coordinate bond i.e. BOTH electrons come from the ligand:
The complex can be drawn in several ways. The arrows in the left hand structure represent the dative
bonds from the water.

The complex on the right is just an octahedral style shape that you drew in the shape topic at AS.

Commonly, a shorthand way is used to write out the complex: [Fe(H2O)6]2+).

The complexes are charged, which depends on both the metal ion and the ligands (see part 2 for more on
this).

think of the complex ion as just another positive ion such as Na +. There is a counter ion (a negative
ion) in all these complexes just as Na+ might have Cl-. It is usually not included as the emphasis of the
topic is the complex ion. Just be aware that if the complex has a 2+ charge, there must be a 2-
somewhere to balance it e.g. SO42-

Types of Ligand
A monodentate ligand has only ONE lone pair of electrons or a negative charge e.g. H2O, Cl-, NH3 and CN-.

Bidentate has two lone pairs: NH2CH2CH2NH2 is ethane-1,2-diamine and the lone pairs are on the
nitrogen atoms at both ends.

This means that it can coordinate (bond to) the metal atom at both ends i.e. one molecule forms TWO
bonds.

Another common one is C2O42-:

So to form an octahedral complex, you would only need 3 of these molecules.

the oxygen aroms bonded to the Cu still have the charge on them:
Multi or polydentate means a ligand has more than 2 lone pairs: EDTA is the common example, which
has 6 lone pairs.

You dont need to know the structure of it. But here it is below. It has four oxygen atoms with negative
charges so it should be written as EDTA4-.

The two nitrogen atoms are neutral but have lone pairs. It will form 4 bonds from the oxygen atoms and
2 bonds from the nitrogen atoms to the metal (6 bonds in total).

Haemoglobin is another multidentate structure.

It is an octahedral complex, with Fe2+ as the metal. The ligand (haem group) has 4 nitrogen atoms bonded
to the Fe2+. The main point is that there is one free site available for O2 and the other is taken up by
globin.

The purpose of haemoglobin is to transport O2 around the body. Problems arise when CO is present as it
is poisonous and forms stronger bonds to the Fe2+ than O2 does so there is competition to occupy the site
to coordinate with the Fe.