A transition element is a d-block element which forms one or more stable ions with an incompletely

filled d sub-shell

A d-block element is one which has electrons filling the d-orbitals. Not all d-block elements are transition
elements as by definition, they must have an incompletely filled d subshell but zinc and scandium do not.

• Scandium forms only one ion (Sc3+) and thus has no electrons in its 3d sub-shell: [Ar] 3d0 4s0.
• Zinc forms only one ion (Zn2+) and thus has a complete 3d sub-shell: [Ar] 3d10 4s0.

When filling the orbitals, the 4s is filled before the 3d (Aufbau). both sub-shells have similar energy level
which allows electrons to be promoted/demoted from one sub-shell to another easily. The 2 exceptions are
for chromium and copper where the 3d is filled before the 4s.
This is linked to the fact that [Ar] 3d5 4s1 (chromium) and [Ar] 3d10 4s1 (copper) configurations
are energetically more stable as in the first case, the d sub-shell is half-filled (singly filled) and in the second
case, the d sub-shell is completely filled.
Shape of d-orbitals
Below are the shapes of the different d-orbitals.

Of course, you don’t have to draw them like this. They can be drawn as shown below:

Note: Pay close attention to the labels on the axes you will draw. Also, you will not be asked to sketch the
dx2-y2 orbital.

Properties of transition elements

1. Physical properties

• High melting points (metallic bonds in transition elements are stronger, 3d+4s electrons involved).
• High densities (Ar higher but radii smaller, more mass per volume).
• Hard and rigid (strong metallic bonding).
• they are good conductors of electricity and heat.
 2. Characteristic properties

• Have variable oxidation states.

• Form coloured ions.
• Form complex ions
• Can act as catalysts.

Explanations

Variable oxidation states

Transition elements have variable oxidation states. For example, iron can exist in 0, +2 or +3 oxidation state.

This is because the 4s and 3d electrons have very similar energy levels, therefore the transition element can
easily lose or gain electrons from one or both sub-shells to form ions with relatively the same stabilities.

Tips: i) The maximum oxidation state of a transition element can be obtained by counting the number of
4s and unpaired 3d electrons. Only copper breaks this pattern.

ii) For small oxidation states, the transition element exists as simple Ma+ ions. For large oxidation states,
the transition element normally exists as an oxo-compounds [contains O2-]. This is because the positive
ions formed by the transition element will have a very high charge density and it will polarise adjacent
molecules (water, oxygen) to form the oxo-compounds.

For example, Cr⁶⁺ does not exist on its own but chromium with oxidation state +6 exists as CrO42⁻.

Catalysts

Transition elements can undergo redox reactions and act as catalysts in many reactions because they can
have multiple stable oxidation states with their energetically accessible vacant d orbitals. Refer to the
previous chapters. [remember the reaction between I- and S2O82- catalysed by Fe2+, homogeneous catalysis]

Ligand and complex

A ligand is a molecule or ion with a lone pair of electrons, capable of forming a co-ordinate bond with a
central metal atom or ion.

Some examples of ligands are water (H2O), ammonia (NH3) and chloride ion (Cl-).

A complex is a molecule or ion containing a central metal ion surrounded by one or more ligands.

Some examples of complexes are [Al(H2O)6]3⁺ and [Fe(H2O)6]3⁺.

Formation of a complex

A complex is formed when ligands bond with a central metal ion via co-ordinate bonding.

For small ligands such as water and ammonia, six is the maximum number of ligands it can bond to a central
metal ion.
For larger ligands such as chloride ions, it can only form four coordinate bonds with a central metal ion.
 • The co-ordination number of a complex is the total number of co-ordinate bonds the ligands form
with the central metal ion.

• Metal complexes are possible because the transition metal element has vacant d orbitals that are
energetically accessible and hence can accommodate the electrons that the ligand(s) will donate.

Ligands will donate lone pairs of electrons. Some ligands can donate 1 lone pair, some can give 2 lone pairs
and some can even give more.

A ligand is said to be monodentate if it forms one co-ordinate bond with the central metal ion only.

Water, ammonia, cyanide ion and chloride ion are monodentate ligands.

A ligand is said to be bidentate if it forms two co-ordinate bonds with the central metal ion.

1,2-diaminoethane and ethandioate ion are bidentate ligands.

You can use the prefixes to specify how many lone pairs the ligand can give: tetradentate, hexadentate…

Ligands giving multiple lone pairs are known as polydentate ligands.

EDTA4- is a polydentate ligand (hexadentate)

The bond angle in the complex depends on the shape of the complex:

• Linear = 180°
• Square planar = 90°
• Tetrahedral = 109.5°
• Octahedral = 90°

Stereoisomerism

There can be geometrical and optical isomerism in metal complexes.

Optical isomerism

Both are chemically the same but they are mirror images of each other and not superimposable. Therefore,
they exhibit optical isomerism.

Geometrical isomerism

Cis-platin Trans-platin

Cis-platin is used as an anti-cancer drug. It binds to the DNA of cancerous cells, preventing them from
dividing and reproducing.

Note: the IUPAC name of platin is diaminedichloridoplatinum(II)

Ligand exchange

A ligand exchange reaction is a reaction in which one ligand in a complex ion is replaced by a different one.

The ligands in a complex can be exchanged, wholly or partially. When a transition element is ionized in a
solution, the truth is that it is most probably is surrounded by H2O ligands. Consider Cu2+ for example:

In reality, it must exist as [Cu(H2O)6]2+. The Cu2+ is surrounded by 6 H2O ligands. This is what causes the blue
colour to a Cu2+ solution. Now if another ligand is added to the solution, a ligand exchange can occur.
If concentrated HCl is added, the chloride ion ligand can replace the H2O ligand [Cl- is bigger that H2O and
hence, will have coordination number 4 instead of 6 that H2O had].

[Cu(H2O)6]2+ + 4Cl– ⇌ [CuCl4]2– + 6H2O

[CuCl4]2– is yellow in colour, hence, a change in colour of the solution from blue to yellow will be observed.

Likewise, if NH3 [in the form of NH4OH] is added to [Cu(H2O)6]2+, first the OH- ions will replace 2 H2O ligands
from the complex resulting in a pale blue ppt.

[Cu(H2O)6]2+(aq) + 2OH–(aq) ⇌ Cu(OH)2(H2O)4(s) + 2H2O(l)

Consequently, if excess NH3 is added, the NH3 will now replace the 2 OH- and 2 H2O ligands. The resulting
complex is soluble but is deep blue in colour. What will be observed is that the pale blue ppt dissolves, giving
a deep blue solution.

Cu(OH)2(H2O)4(s) + 4NH3(aq) ⇌ [Cu(H2O)2(NH3)4]2+(aq) + 2H2O(l) + 2OH–(aq)

Note: do not forget to balance the complex charges as you go. For CuCl4 it is 2- as Cu is 2+ and 4x Cl- = -4.
The sum is -2. For the ppt Cu(OH)2(H2O)4(s), it has no charge as Cu is 2+ and 2x OH- = -2. The sum is zero. That
is also a reason why it precipitates.

The same principle applies to cobalt. Whenever we write Co2+(aq), we are referring to the complex ion
[Co(H2O)6]2+.

[Co(H2O)6]2+ is pink in colour.

If OH- is added, just like for copper, 2 H2O ligands are replaced to give Co(OH)2(H2O)4(s) which is blue-green
(or also pink it depends) in colour. It is a precipitate. [Note: the ppt will turn pink on standing after some
time].

Adding NH3 to [Co(H2O)6]2+ will result in all the H2O ligands to be replaced by NH3.

[Co(H2O)6]2+(aq) + 6NH3(aq) ⇌ [Co(NH3)6]2+(aq) + 6H2O(l)

[Co(NH3)6]2+(aq) is straw-coloured.

Adding concentrate HCl will 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)

Stability constants

As you can see above, complex formation is reversible and hence, an equilibrium constant Kc can be
obtained.

Just like for the other equilibrium constants, we remove the [H2O] as it is a constant and hence, we will
obtain a new constant that we will call the stability constant, Kstab.

Example: for the complex formation [Cu(H2O)6]2+ + 4Cl–(aq) ⇌ [CuCl4]2–(aq) + 6H2O(l)

The unit of Kstab has to be calculated just like for the other equilibrium constant. The greater the Kstab value
means that the complex is more stable and favoured compared to one with a smaller Kstab value.

Visible light is the visible part of the electromagnetic spectrum which has wavelengths between 400 nm to
700 nm. White light is composed of all the wavelengths in the visible part of the electromagnetic spectrum.

When white light passes through a complex, for example copper(II) sulfate, CuSO4 solution, visible light with
wavelengths in the red-orange-yellow region is absorbed. The unabsorbed ones continue their path and is
the colour we will observe with our eyes which is in this case blueish.

The colour observed in a metal complex is the complementary colour of the wavelength (colour) of the
light absorbed by the metal complex.
Using the colour wheel, we can estimate the colour absorbed.

The why

In elemental state, the transition elements have d orbitals of the same energy. They are called degenerate.

Degenerate orbitals are orbitals having the same energy

In ionized state, the d sub-shell does not stay degenerate and will split in 2 set of orbitals of equal energy.
They are called non-degenerate.

Non-degenerate orbitals are orbitals not having the same energy

The splitting will depend on the shape of the complex and hence the ligand involved. dxy, dxz and dyz will be
together while dz2 and dx2-y2 will be together. This is due to the nature of the orbitals. dxy, dxz and dyz are
found in between the axes while dz2 and dx2-y2 are found on the axes.

This means that tetrahedral bonding involves dxy, dxz and dyz as they are in between axes and octahedral
bonding involves dz2 and dx2-y2 as they are found on the axes, thus raising their respective energies.

The d sub-shell will split as shown on the next page.

 Octahedral Tetrahedral

For an octahedral complex, the central metal ion has five degenerate d-orbitals. They split into two groups,
two with higher energy and the other three with lower energy when ligands are attached to it. This is because
as the lone pairs on the ligands approach the central metal ion, the d-electrons in the central metal ion are
repelled. Due to the shape of the octahedral complex, the d-electrons repelled are the ones in the dz² and
dx²-y² orbitals, and these orbitals will have higher energy.

For a tetrahedral complex, the central metal ion has five degenerate d-orbitals. They split into two groups,
three with higher energy and the other two with lower energy when ligands are attached to it. This is because
as the lone pairs on the ligands approach the central metal ion, the d-electrons in the central metal ion are
repelled. Due to the shape of the tetrahedral complex, the d-electrons repelled are the ones in the dxy, dxz
and dyz orbitals, and these orbitals will have higher energy.

Note: relatively speaking, the 2 sets of orbitals forms have higher energy that the degenerate d sub-shell.

Average
energy of the
separated
orbitals Separated
Original d d orbitals
sub-shell

As seen, for the separated d-orbitals, one is higher, the other one is lower but still, both are above the original
d sub-shell level.
The gap between the split d orbitals, ΔE, depends on:

• the oxidation state of the central metal ion.

• the nature of ligands

No need to
know by
heart

The reason the complexes have a colour is that the electrons can get promoted from the lower energy level
to the higher energy level of the 2 non-degenerate d orbitals when they absorb light (photons) with energy
of ΔE. The resulting colour of the complex is the complimentary colour of the frequency of light absorbed.

This is called a d-d transition.

To calculate the value of ΔE, we use the following formula:

ΔE = hf

Where h is the planck’s constant [6.626x10-34 JHz-1]

f is the frequency of the light absorbed

For transition elements, the frequency of light absorbed is found in the visible region of the electromagnetic
spectrum. Hence, we can see that transition metal complex are coloured.

The colour of the complex is the result of the unabsorbed frequencies of light combining together.

Anything that can change the value of ΔE will affect the colour of the complex, may it be the ligand or the
oxidation state of the metal ion or else.