Colour and complex metal ions

Narrabundah College
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Transition Metals
There are a number of different models which explore the characteristics and behaviours of transition
metal ions and their complexes. Crystal field splitting and Valence Bond theory are some of these.

Valence bond theory can be useful to explain shapes of complexes, and there is some evidence that
there is some covalent character to the bonds between ligands and the metal/s ions. But to explain
colours of transition metals and their complexes and paramagnetism it is more useful to use crystal field
theory. Again, this is based on the idea that most characteristics can be explained by consideration of
where electrons are and how they move.
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Transition Metals: Crystal Field Theory

In Crystal Field Theory the metal ion and ligands can be treated as point charges and the spatial arrangement
of these point charges affects the energies of the d-orbitals of the central metal atom. Ligands donate electron
density into these orbitals to form the bonds, the attraction is all electrostatic. This assumes the bonding
between the metal and the ligand is ionic, electrostatic attraction, rather than covalent. In CFT the ligands, as
point charges, would have ion-ion attractions to the metal, if the ligand is neutral the attraction would be ion-
dipole interaction. These attractions provide stability and hold the complex together.

The presence of the ligands influences the energy levels of the d-orbitals.

All ligands will donate electron density, and this electron density will repel the electron density on the metal.
Due to this repulsion certain d-orbitals will have their energies increased, but not to the same extent.

Consider the response of the d-orbitals to the approach of six ligands along the x, y and z axes of the metal.
What do we need to look at?

The shapes of the atomic d-orbitals (which are degenerate in the isolated metal) and orientations of those
atomic d-orbitals along the axes.
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Transition Metals: Crystal Field Theory

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Transition Metals: Crystal Field Theory

We will consider the case of octahedral complexes first.

When the metal and the ligands are separate from each other they are at a higher energy level. When the
metal/ion and ligand form a complex they are a more stable entity.

But there is still some repulsion between the ligand’s bonding electrons and the d-orbitals electrons.

As ligands approach along the axes (maximising their distance from each other), the greatest interaction
between the ligands and the d-orbital electrons is along the axes and the d-orbitals that lie along the axes are
more strongly affected than those that lie between the axes.

The d-orbital energies are split by the ligands.

The degree to which they are split, the distance between the split orbitals, depends on the

• oxidation state of the metal

• nature (eg size) of the metal ion

• number and geometry of the ligands

• nature (strength) of the ligands

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Transition Metals: Crystal Field Theory

Electrostatic interaction
between ligand and metal.

The ligands approach along the

axes, the greatest interaction
between the ligands and the
metal orbitals is along the axes,
so these orbitals are affected the
most. The more directly the
ligand attacks the metal orbital,
the higher the energy of the d-
orbital.

In an octahedral field the energy

of the five d-orbitals is split in a
distinctive way.
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Transition Metals: Crystal Field Theory

d-orbital and ligand interaction (octahedral
field).

The dz2 and dx2 – y2 orbitals lie on the

same axes as the ligand negative
charges; therefore, there is a large,
unfavourable interaction between
ligand and orbitals. These orbitals
form the degenerate high energy pair
of energy levels.
The dxz , dyz and dxz orbitals bisect the
negative charges; therefore, there is
a smaller repulsion between ligand
and metal for these orbitals. These
orbitals form the degenerated lower
energy set of energy levels.
In an octahedral complex the d-
orbitals are split, two up and three
down.
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Transition Metals: Crystal Field Theory

Octahedral field Splitting Pattern:
The energy gap between the split d-orbitals is referred to as Δ, the crystal field splitting energy. The magnitude of Δ
depends on
1 Metal: larger metal, larger Δ
higher oxidation state, larger Δ
2 Ligand: position in the Spectrochemical series (strength of Ligand)
I- < Br- < Cl- < F- < OH- < H2O < C2O42- < NH3 < en < NO2-< (N-bonded) < CN- < CO

Weak field ligand: low Strong field ligands: High

electrostatic interaction electrostatic interaction
small crystal field splitting large crystal field splitting.

In the middle of the series are ligands such as en and NH3 which are not considered to be strong field or weak field
ligands, the magnitude if Δ depends on the metal charge ( a high metal oxidation state results in a large Δ) and the
size of the metal (Δ for the first row of the transition metal is generally smaller than Δ for second and third row
transition metals).
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Transition Metals: Crystal Field Theory

Octahedral field Splitting Pattern: electrons in the split d-orbitals
Electron configuration of the metal ion: s-orbital electrons are lost first, then the d-orbital electrons.
Ti3+ is a d1, V3+ is a d2 and Cr3+ is a d3 .
Using Hund's Rule- electrons fill singly into lowest energy orbitals available, these 3 electrons would fill into the
lower three d-orbitals.
Where do the 4th , 5th , 6th or 7th electron go? There is a choice, and it depends on how large Δ is.
If the split is small this next electron goes into the available higher orbital, this arrangement is called high spin
If the is split is large this next electron goes into the lower set of orbitals, this arrangement is called low spin
The term high spin refers to arrangement of electrons having the maximum number of unpaired electrons
possible, while low spin refers to the arrangement with the lesser number of unpaired electrons.
Weak field ligands have small Δ and tend to form high spin complexes.
Strong field ligands have large Δ and tend to form low spin complexes.
Care needs to be taken when designating high spin or low spin arrangements to different complexes
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Transition Metals: Crystal Field Theory

Octahedral field Splitting Pattern: electrons on the split d-orbitals
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Transition Metals: Crystal Field Theory

Octahedral field Splitting Pattern: electrons in the split d-orbitals

Electron configuration for octahedral complexes of metal ions having d1 to d10 configuration on [M(H2O)6]n+

Only d4 through to d7 cases can have both high spin and low spin configuration, depending on the ligand.
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Transition Metals: Crystal Field Theory

Splitting Pattern other field patterns : to know.

The d-orbital splitting patterns

for tetrahedral complexes and
square planar are different to
the octahedral splitting pattern .
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Transition Metals: Crystal Field Theory

Splitting Pattern other field patterns : to know.
The d-orbital splitting pattern for tetrahedral
complexes has two orbitals at lower energy
and three at higher energy.
Tetrahedral ligands interact with the orbitals
differently to octahedral complexes, so we get
different energy diagrams; ligands more closely
approach the dxy/dxz/dyz orbitals, between the
axes rather than orbitals along the axes.
Ligands don’t approach the orbitals as directly
so the electrostatic interactions are not as
strong, therefore the final energy levels are
lower than with octahedral complexes and they
don’t produce as large splitting.
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Transition Metals: Crystal Field Theory

Splitting Pattern other field patterns : to know.

The d-orbital splitting patterns for

square planar complexes have a
different arrangement, with a larger
gap to the highest orbital.
Square planar ligands approach dx2-y2
very directly on the axes and force this
orbital to a higher energy level.
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Transition metal d-orbital splitting

Splitting of d-
orbitals due to the
presence of ligands
and the change in
the splitting moving
from octahedral to
square planar.
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Transition Metals: Crystal Field Theory

Splitting Pattern other field patterns : for interest only.
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Transition Metals
What should a bonding theory explain? Why are most transition metal complexes brightly coloured, but some are not?
What is colour? (White light: EM radiation consisting of all λ’s in the visible range)

Objects appear coloured in white light because they absorb certain λ’s and transmit (or reflect) the λ’s not absorbed.
The transmitted (or reflected) light gives us the perceived colour.

If an object absorbs all λ’s the colour we see is black. If an object reflects all λ’s then the colour we see is white.

If an object absorbs al λ’s except green, the reflected (transmitted) light is green.
If an object absorbs only red (complimentary colour of green) the remaining mixture of reflected (transmitted) λ’s is
seen as green.
When a sample absorbs light, what we see is the sum of the remaining (not absorbed) colours that strike our eyes
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Transition Metals

only orange reflected only blue absorbed

If the sample absorbs all BUT orange, the sample appears orange. We also perceive orange colour when visible
light of all colours except blue strikes our eyes. Orange and blue are opposite colours on a colour wheel, called
complimentary colours. We see the colour that is complimentary to that which is absorbed. If a sample absorbs
orange we see blue, if a sample absorbs blue we see orange. (although it may not always be so simple)
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Transition Metals
Relationship between absorbed and observed colours

Absorbed Observed
λ (nm) λ (nm)
colour colour

Violet 400 Green-yellow 560

Blue 450 Yellow 600

Blue-green 490 Red 620

Yellow-green 570 Violet 410

Yellow 580 Dark blue 420

Orange 600 Blue 450

Red 650 Green 520

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Transition Metals: Crystal Field Theory

Octahedral field Splitting Pattern:
The energy gap between the split d-orbitals is referred to as Δ, the crystal field splitting energy. The magnitude of Δ
depends on
1 Metal: larger metal, larger Δ
higher oxidation state, larger Δ
2 Ligand: position in the Spectrochemical series (strength of Ligand)
I- < Br- < Cl- < F- < OH- < H2O < C2O42- < NH3 < en < NO2-< (N-bonded) < CN- < CO

Weak field ligand: low Strong field ligands: High

electrostatic interaction electrostatic interaction
small crystal field splitting large crystal field splitting.

In the middle of the series are ligands such as en and NH3 which are not considered to be strong field or weak field
ligands, the magnitude if Δ depends on the metal charge ( a high metal oxidation state results in a large Δ) and the
size of the metal (Δ for the first row of the transition metal is generally smaller than Δ for second and third row
transition metals).
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Transition Metals: Crystal Field Theory

d-orbital splitting and colour :

Many main group ionic compounds are colourless because the metal ion has a filled outer shell and electron transitions, in
the visible range, are not possible. For the transition metals, with partially filled d-orbitals, the electrons can absorb λ’s of
visible light as they move from lower energy orbitals to a higher energy d-orbitals, this is called d-d transitions. Therefore,
many transition metal complexes have striking colours. This is because the d-orbital energies are split, and the energy
required for electron transition is in the range of white light. Electrons absorb the energy of a particular colour to be
promoted to a higher energy level and we see the complimentary colour that is not absorbed.
The following are colourless, as their d-orbitals are empty or completely filled, : Sc3+ or Ti4+ [Ar] 3d0 or Zn2+ [Ar] 3d10 .
 Transition Metals: Crystal Field Theory
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d-orbital splitting and colour :

These d-d electronic transitions can be explained by the electron configuration of the metal and the magnitude of Δ. It is important to
note, however, that other electronic transitions are possible that absorb energy outside the visible range and that not all possible d-d
transitions are “allowed”. A d-d transition that results in a change in the number of unpaired electrons, or where the electron would
change spin, (ΔS≠0), are “spin forbidden” , and therefore the observed colour for these transitions is not very intense.
Example 1: Why is an aqueous solution of [Ni(NH3)6]2+ deep blue while and aqueous solution of [Ni(H2O)6]2+ is green?

Both complex ions contain Ni2+ and are octahedral but with different ligands.
NH3 will produce a larger Δ than H2O, and the complex with the larger Δ will
absorb light with the higher energy (shorter λ’s ).

[Ni(H2O)6]2+ solutions [Ni(NH3)6]2+ solutions

are green as they have are blue as they have
smaller Δ and absorb larger Δ and absorb
lower energy red light. orange –yellow light.

Example 2: Why are aqueous solutions of Mn2+ nearly colourless?

Mn2+ has five unpaired electrons. In an octahedral complex it can be either high spin or low spin. The fact

that it is nearly colourless tells us that the ion is high spin because d-d transitions are “spin forbidden” for this

electron configuration.
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Transition Metals: Crystal Field Theory

d-orbital splitting and colour : effects of metal oxidation state and of ligand identity on colour
For a given ligand, the colour depends on the
oxidation state of the metal ion
Both the vanadium complexes shown have the
same ligand but the oxidation state of the metal
changes from +2 to +3. This means there the
more highly charged ion draws the charge cloud in
more closely, so give greater electrostatic
interaction. With a larger Δ , a larger amount of
energy is absorbed, so a different λ of light
absorbed and therefore a different colour is seen.

For a given metal ion, the colour depends on

the ligand.
With the two solid complexes, the metal ion is the
same but the ligands are different, and therefore
the degree of splitting of the d-orbitals, is different.
With a different degree of splitting, the λ of light
absorbed to promote the electrons would be
different, therefore a different colour is seen.
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Transition Metals: Crystal Field Theory

d-orbital splitting and colour : effects of metal
oxidation state and of ligand identity on colour

For a given ligand, the colour depends on the

oxidation state of the metal ion and the metal identity.
Different metal ions with H2O as the ligand show
different colours.

The solids here are all the same metal ion, Co3+ , but
as the ligands are different and produce a different
degree of splitting , then the colours seen are
different.
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Transition Metals: Crystal Field Theory

d-orbital splitting and colour :

Spectrochemical series: increasing Δ

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Transition Metals: Crystal Field Theory

d-orbital splitting and colour : the colours of some of the complexes of the Co3+ ion

The complex with fluoride ion, [CoF6]3-, is high spin and has one absorption band. The other complexes have two
absorption bands. In all but one case, one of these absorptions is in the visible region of the spectrum. The
wavelengths refer to the centre of the absorption band
Wavelength of Light Colour of Light
Complex ion Colour of complex
Absorbed (nm) Absorbed

[CoF6]3- 700 red green

[Co(C2O4)3]3- 600 , 420 yellow , violet dark green

[Co(H2O)6]3+ 600 , 400 yellow , violet blue-green

[Co(NH3)6]3+ 475 , 340 blue , violet yellow-orange

[Co(en)3]3+ 470 , 340 blue , ultraviolet yellow-orange

[Co(CN)6]3- 310 ultraviolet pale yellow

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Transition Metals: Crystal Field Theory

Key Concepts
Crystal field theory explains why the d orbitals in a coordination compound are not equal in energy, the presence of
the ligands splits the energy of d orbitals.

The octahedral crystal field splitting energy, Δ, can be larger than electron-pairing energy (a strong-field case) or
smaller than electron-pairing energy (a weak-field case).

For coordination compounds with four to seven d electrons, high-spin (small Δ) and low-spin (large Δ) electron
configurations are possible.

The spectrochemical series shows the effect ligands have on the magnitude of Δ; compounds containing strong-
field ligands generally have a large Δ, whereas compounds containing weak-field ligands generally have a small Δ.

Coordination compounds are colored because of d–d transitions, where electrons move from lower-energy d
orbitals to higher-energy d orbitals.

The color of a coordination compound is the complementary color of the light absorbed by the compound.

Not all d–d transitions are allowed or absorb light in the visible region of the electromagnetic spectrum.