COMPLEX IONS

At the end of the lesson, you should be able to:

 Describe and explain the reactions of transition elements with ligands to form complexes, including the
complexes of copper(II) and cobalt(II) ions with water and ammonia molecules and hydroxide and chloride ions
 Define the term ligand as a species that contains a lone pair of electrons that forms a dative bond to a central
metal atom/ion including monodentate, bidentate and polydentate ligands
 Define the term complex as a molecule or ion formed by a central metal atom/ion surrounded by one or more
ligands
 Describe transition metal complexes as linear, octahedral, tetrahedral or square planar
 State what is meant by co-ordination number and predict the formula and charge of a complex ion, given the
metal ion, its charge, the ligand and its co-ordination number

➢ A ligand is a species that contains one or more lone pairs of electrons that forms dative covalent bonds with
the central metal ion
➢ A ligand behaves as a Lewis base by donating an electron pair to the central metal ion of a complex ion.
➢ The transition metal ion behaves as a Lewis acid by accepting the electron pair from the ligand
➢ Complex ion is formed when central metal atom/ion combines with surrounding ligands (contain at least a
lone pair of electrons available for donation to the vacant orbitals of the central metal atom /ion) by dative
bonds.
➢ Coordination number: The number of coordinate or dative covalent bonds to the central metal ion.
• Different metal ion shows different coordination number with the same ligands
➢ Transition metals form complexes because:
• The metal ions are small in size so they have a strong electric field around them which attracts the
electron-rich ligands
• They have vacant 4s and 4p orbitals that are hybridised and can accept electrons.

Types of Ligands
➢ There are 3 categories of ligands:

Monodentate Bidentate Multidentate

A ligand that forms only one dative A ligand that forms two dative bonds A ligand that forms more than
bond with central metal ion with central metal ion two dative bonds with central
(each ligand molecule donates a (each ligand molecule donates 2 metal ion (each ligand molecule
pair of electrons) pairs of electrons) donates three or more pairs of
electrons)
For example: H2O, NH3, Cl- , CN- For example: NH2CH2CH2NH2, C2O42- For example: EDTA4-
(ethylenediaminetetraacetic acid

Writing Formulae of Complexes

• The metal ion must be written first followed by the ligands.
• Place charge on formula in square brackets with anion ligands coming before neutral ligands.
• Total charge on complex = sum of charge on metal ions and charge on ligand (if ligands are all neutral, charge
on complex= charge on metal ion)
Naming Complexes
➢ Cations are always named before the anions (just like naming an ionic compound).
➢ Name the ligands first, in the following order: neutral, negative, positive. If there are multiple ligands in
alphabetical order:

Anionic Ligands Neutral Ligands

Br- Bromo NH3 Ammine
F- Fluoro H2O Aqua
O2- Oxo NO Nitrosyl
CN- Cyano CO Carbonyl
OH- Hydroxo
• Multiple occurring monodentate ligands receive a prefix mono-, di-, tetra-, penta- and hexa-. For bidentate
or multidentate ligands – use prefixes mono-, bis-, tris-, tetrakis-, pentakis-.
• After naming the ligands, name the central metal ion:
• If the complex ion is a cation (positive charge), the metal is named same as the element.
For example:
• If the complex ion is an anion (negatively charged), the metal name will end with the suffix -ate.
Metal Anion name
Iron Ferrate
Copper Cuprate
Lead Plumbate
Silver Argenate
Gold Aurate
Tin Stannate

• For example:
1) [Cu(H2O)6]2+ - hexa aqua copper(II) ion
2) [Cu(Cl)4]2- - tetrachlorocuprate(II) ion

SHAPES OF COMPLEXES

Coordinate
Shape Examples Diagram
No.

[CuCl2]2-
2 Linear
[Ag(NH3)2]+

4 Square Planar [Ni(CN)4]2-

[CoCl4]2+
4 Tetrahedral
Ni(CO)4

[Fe(H2O)6]2+
6 Octahedral
[Co(H2O)6]2+
 Stereoisomerism in Transition Element Complexes
Objectives:
At the end of the lesson, you should be able to:
• Describe the types of stereoisomerism shown by complexes, including those associated with bidentate
ligands:
• (i) cis-trans isomerism, e.g. cis- and trans-platin Pt(NH3)2Cl2
• (ii) optical isomerism, e.g. [Ni(NH2CH2CH2NH2)3]2+
• Describe the use of cisplatin as an anticancer drug and its action by binding to DNA in cancer cells, preventing
cell division

• Previously in AS Level, we learned that there are two types of stereoisomerism: geometric isomerism and optical
isomerism.
• In stereoisomerism, the molecules have same molecular formula and structural formula but the isomers have
different spatial arrangement of atoms.
• Geometric isomerism is possible in transition element complexes, where no double bond exists.
For example:

➢ In cis-platin, the chlorine atoms are next to each other in

the square complex but in trans-platin, they are opposite.
➢ The properties of these geometrical isomers are slightly
different.
➢ Cis-platin has been used as an anti-cancer drug.
➢ Cis-platin binds to sections of the DNA in cancer cells,
preventing cell division.

• Stereoisomerism is commonly shown by octahedral (six co-ordinate) complexes associated with bidentate
ligands.
For example: Nickel transition metal ion and 1,2-diaminoethane (NH2CH2CH2NH2)

➢ The two isomers on the right are

stereoisomers – they are mirror
image of one another and cannot be
superimposed.
➢ The isomer on the right rotates the
polarised light clockwise so this
isomer is referred to as (+)
dextrorotary or the (S)-enantiomer
whereas the isomer on the left
rotates the polarised light anti-
clockwise so this isomer is referred
to as (-) levorotary or the (R)-
enantiomer

Simplified structure of [Ni(en)3]2+ (aq) ion

 Ligand Substitution
Objectives:
At the end of the lesson, you should be able to:
 Describe and explain ligand exchanges in terms of competing equilibria
 Describe the term stability constant, Kstab, of a complex ion in a solvent from its constituent ions or molecules
 Deduce expressions for the stability constant in ligand substitution
 Explain ligand exchange in terms of stability constants and understand that a large value of K stab is due to the formation
of a stable complex ion

• Substitution of ligands is when a ligand replaces other ligand in a transition metal complex.
• Even though the transition metal complex ion is stable, the metal ion itself is still attracted to the surrounding ligand.
• Ligands can be replaced by other molecules that are able to donate a pair of electrons.
• For A level, the three most common ligands are water (H2O), ammonia (NH3) and chloride (Cl-).

Substitution of water ligands with chloride ions in [Co(H2O)6]2+

• In aqueous state, Cobalt (II) ion is surrounded by six water ligands

octahedrally.
• Addition of concentrated hydrochloric acid to the solution will cause the
solution to change its colour from pink to rich blue.
• This is due to 6 water ligands are replaced by 4 chloride ions to form a
tetrahedral complex ion [CoCl4]2-

• The different sizes of water molecules and Cl- that ligand exchange takes
place with a change in coordinate number.
• This reaction can be easily reversed by adding water to the solution.
• Addition of water to the right-hand side of the equilibrium has the effect of moving the position of equilibrium to the left,
restoring the pink colour of the hexaaquacobalt(II) ion (paler pink as it is more dilute).

Substitution of water ligands with ammonia in [Cu(H2O)6]2+

• When a small amount of ammonia is added to a solution of

[Cu(H2O)6]2+, a pale blue precipitate of [Cu(H2O)4(OH)2 ] will form.
• Addition of excess ammonia will result in the precipitate to be soluble
and form a dark blue solution.
• The similar sizes of water and ammonia molecules ensure that ligand
exchange takes place with no change in coordination number
(the complex ion remains as
octahedral structure).

Excess NH3

Substitution of water ligands with SCN- ions in [Fe(H2O)6]3+

• Addition of thiocyanate ions, SCN-, to a solution containing iron(III) ions will result in a colour
change of the solution from yellow to intense blood red solution containing the ion
[Fe(SCN)(H2O)5]2+.
[Fe(H2O)6]3+ + SCN- → [Fe(H2O)5(SCN)]2+ + H2O
• Only one water ligand is replaced by the SCN- ion and there is no net change in
coordination number in the complex ion.

Substitution of water ligands with hydroxide ions in [Zn(H2O)6]2+

• When a small amount of NaOH (aq) is added to a solution of

[Zn(H2O)6]2+, a white precipitate of [Zn(H2O)4(OH)2 ] will form.
• Addition of excess ammonia will result in the precipitate to be
soluble and form a colourless solution of [Zn(OH)4]2-
 Stability of Complex Ions, Kstab
Objectives:
At the end of the lesson, you should be able to:
 Describe and explain ligand exchanges in terms of competing equilibria
 State that the stability constant, Kstab, of a complex ion is the equilibrium constant for the formation of the complex ion
in a solvent from its constituent ions or molecules
 Deduce expressions for the stability constant of a ligand substitution
 Explain ligand exchange in terms of stability constants, Kstab, and understand that a large Kstab is due to the formation
of a stable complex ion
➢ Aqueous solutions of transition element ions are hydrated – they are complex ions with water as ligands.
➢ The stability of complex ions depends on the ligands.
For example:
[Cu(H2O)6]2+ (aq) + NH3 (aq) [Cu(NH3)(H2O)4]2+ (aq) + H2O (l)
2+
[Cu(NH3)2(H2O)4] (aq) + NH3 (aq) [Cu(NH3)2(H2O)4]2+ (aq) + H2O (l)
• As we increase the concentration of ammonia, the process continues until all water ligand is replaced to form a
deep blue solution.
[Cu(H2O)6]2+ (aq) + 4 NH3 (aq) [Cu(NH3)4(H2O)2]2+ (aq)
• Stability constant, Kstab is the equilibrium constant for the formation of complex ion in a solvent from its constituent
ions or molecules.
Take note: Water is not included in the Kstab expression because it is in large excess that its concentration is regarded
as constant. The units for the stability constant are worked out in the same way as for the units for K c.
• Stability constants are often given on a log10 scale (no units) – the higher the value, the more stable the complex is.
• Stability of the ligands decreases from multidentate to monodentate.
• Multidentate ligands have a better chelating effect (stabilising) than bidentate and monodentate ligands.
• Entropy is the reason to chelate effect since the enthalpy change is similar.
• For example:

❖ In the equilibrium above, substitution of two water ligands with a 1,2-diaminoethane ligand increases the
entropy of the system (by increasing the number of molecules on the products side).
❖ In the case of substitution with EDTA4-, the increase in entropy is very significant, hence complexes involving
multidentate ligands are more stable than those with only unidentate ligands in them.

Colour of Complexes
Objectives:
At the end of the lesson, you should be able to:
 Sketch the shape of a d orbital
 Describe the splitting of degenerate d orbitals into two energy levels in octahedral and tetrahedral complexes
 Explain the origin of colour in transition element complexes resulting from the absorption of light energy as an electron
moves between two non-degenerate d orbitals
 Describe, in qualitative terms, the effects of different ligands on absorption, and hence colour, using the complexes of
copper (II) ions with water and ammonia molecules and hydroxide and chloride ions as examples
 Apply the above ideas of ligands and complexes to other metals, given information

• Transition elements can be found in the d-block.

• Most of the transition element compounds are coloured. This is due to the splitting of the d subshell in the transition
metal ion caused by the bonding with the ligands.
• There are five types of d orbitals:
 • The five d orbitals in an isolated transition metal atom or ion are described as degenerate, meaning they are all at
the same energy level.
• When ligands form coordinate bond with the central transition metal ion, the d-orbital splits to form 2 sets of non-
degenerate d orbitals. This depends on the coordination of the ligands in the complex.

Splitting of d-orbitals in Complex ions

• The electric fields associated with the ligands cause repulsions in the d orbitals and that raises their energies.
• The coordination of the ligands also affects the various d orbitals differently depending on how they are arranged in
around the central metal ion
• In octahedral structure, the ligands are attracted to the central metal ions along the x, y and z axis and this results in
the repulsion of the d orbitals on the axis to a higher energy level. Hence the d subshell splits as shown in (b).
• In tetrahedral structure, the ligands are attracted to the central metal ions between the x, y and z axis and this results
in the repulsion of the d orbitals between the axis to a higher energy level.