Complex compounds,their role in analytical chemistry.

Complexonometry

Coordination compounds are chemical compounds that consist of an array of

anions or neutral molecules that are bound to a central atom via coordinate covalent
bonds. Coordination compounds are also referred to as coordination complexes.
These molecules or ions that are bound to the central atom are referred to as ligands
(also known as complexing agents). Many coordination compounds contain a
metallic element as the central atom and are therefore referred to as metal
complexes. These types of coordination complexes generally consist of a transition
element as the central atom. It can be noted that the central atom in these
complexes is called the coordination centre.

Coordination Entity
A chemical compound in which the central ion or atom (or the coordination centre) is
bound to a set number of atoms, molecules, or ions is called a coordination entity.

Some examples of such coordination entities include [CoCl3(NH3)3] and [Fe(CN)6]4-.

Central Atoms and Central Ions

As discussed earlier, the atoms and ions to which a set number of atoms, molecules,
or ions are bound are referred to as the central atoms and the central ions.

In coordination compounds, the central atoms or ions are typically Lewis Acids and
can, therefore, act as electron-pair acceptors.

Ligands
The atoms, molecules, or ions that are bound to the coordination centre or the central
atom/ion are referred to as ligands.

These ligands can either be a simple ion or molecule, such as Cl– or NH3 or in the
form of relatively large molecules, such as ethane-1,2-diamine (NH2-CH2-CH2-NH2).

Coordination Number
The coordination number of the central atom in the coordination compound refers to
the total number of sigma bonds through which the ligands are bound to the
coordination centre.
For example, in the coordination complex given by [Ni(NH3)4]2+, the coordination
number of nickel is 4.

Coordination Sphere
The coordination sphere is the non-ionizable part of a complex compound, which
consists of a central transition metal ion surrounded by neighbouring atoms or
groups enclosed in a square bracket.

The coordination centre, the ligands attached to the coordination centre, and the net
charge of the chemical compound as a whole form the coordination sphere when
written together.

This coordination sphere is usually accompanied by a counter ion (the ionizable

groups that attach to charged coordination complexes).

For example, [Co(NH3)6]C/3 – coordination sphere

Coordination Polyhedron
The geometric shape formed by the attachment of the ligands to the coordination
centre is called the coordination polyhedron.

Examples of such spatial arrangements in coordination compounds include

tetrahedral and square planar.

Oxidation Number
The oxidation number of the central atom can be calculated by finding the charge
associated with it when all the electron pairs that are donated by the ligands are
removed from it.

For example, the oxidation number of the platinum atom in the complex [PtCl6]2- is +4.

Homoleptic and Heteroleptic Complex

• When the coordination centre is bound to only one type of electron pair
donating ligand group, the coordination complex is called a homoleptic
complex, for example, [Cu(CN)4]3-.
 • When the central atom is bound to many different types of ligands, the
coordination compound in question is called a heteroleptic complex, for
example, [Co(NH3)4Cl2]+.

Properties of Coordination Compounds

The general properties of coordination compounds are discussed in this subsection.

• The coordination compounds formed by the transition elements are coloured

due to the presence of unpaired electrons that absorb light in their electronic
transitions. For example, the complexes containing Iron(II)can exhibit green
and pale green colours, but the coordination compounds containing iron(III)
have a brown or yellowish-brown colour.
• When the coordination centre is a metal, the corresponding coordination
complexes have a magnetic nature due to the presence of unpaired electrons.
• Coordination compounds exhibit a variety of chemical reactivity. They can be
a part of inner-sphere electron transfer reactions as well as outer-sphere
electron transfers.
• Complex compounds with certain ligands have the ability to aid in the
transformation of molecules in a catalytic or stoichiometric manner.

Double Salts and Coordination Complex

Double Salts
Double salts are completely ionizable in aqueous solutions, and each ion in the
solution gives the corresponding confirmatory test.

For example, potash alum is double sulphate. It is K2SO4.Al2(SO4)3.24H2O on

ionization, and it gives K+, SO2−4 and Al+3 ions, which respond to the corresponding tests.

Coordination Complex
Coordinate complexes are incompletely ionizable in the aqueous solutions. They give
a complexion which does not show complete ionization.

For example, potassium ferrocyanide. [K4Fe(CN)6]. It ionizes to give K+ and

[Fe(CN)6]−4 [ferro cyanide ions].

Types of Coordination Complexes

 • Cationic complexes: In this coordination, the sphere is a cation. For example,
[Co(NH3)6]Cl3
• Anionic complexes: In this coordination, the sphere is Anion. For example,
K4[Fe(CH)6]
• Neutral Complexes: In this coordination, the sphere is neither a cation nor an
anion. For example, [Ni(CO)4]
• Homoleptic complex: The complex consists of a similar type of ligands. For
example, K4[Fe(CN)6]
• Heteroleptic complexes: These consist of different types of ligands. For
example, [Co(NH3)5Cl]SO4
• Mononuclear complexes: In this coordination, the sphere has a single
transition metal ion. For example, K4[Fe(CN)6]
• Polynuclear complexes: More than one transition metal ion is present.

The surrounding atoms, ions and molecules around the central transition
metal ion are known as Ligands. They act as Lewis bases and donate electron
pairs to transition metal ions; thus, a dative bond is formed between ligands
and the transition metal ion. Hence, these compounds are coordination
complexes.

Types of Ligands
Based on the nature of the bond between the ligand and the central atom, ligands
are classified as follows:

• Anionic ligands: CN–, Br–, Cl–

• Cationic ligands: NO+
• Neutral ligands: CO, H2O, NH3

Ligands can be further classified as:

Unidentate Ligands
The ligands which only have one atom that can bind to the coordination centre are
called unidentate ligands. Ammonia (NH3) is a great example of a unidentate ligand.
Some common unidentate are Cl–, H2O etc.

Bidentate Ligands
Ligands which have the ability to bind to the central atom via two separate donor
atoms, such as ethane-1,2-diamine, are referred to as bidentate ligands.
Polydentate Ligands
Some ligands have many donor atoms that can bind to the coordination centre.
These ligands are often referred to as polydentate ligands.

A great example of a polydentate ligand is the EDTA4- ion (ethylene diamine

tetraacetate ion), which can bind to the coordination centre via its four oxygen atoms
and two nitrogen atoms.

Chelate Ligand
When a polydentate ligand attaches itself to the same central metal atom through
two or more donor atoms, it is known as a chelate ligand. The atoms that ligate to the
metal ion are termed as the denticity of such ligands.

Ambidentate Ligand
Some ligands have the ability to bind to the central atom via the atoms of two
different elements.

For example, the SCN– ion can bind to a ligand via the nitrogen atom or via the sulfur
atom. Such ligands are known as ambidentate ligands.

Werner’s Theory
Alfred Werner, in 1898, proposed Werner’s theory, explaining the structure of
coordination compounds.

Werner’s Experiment: By mixing AgNO3 (silver nitrate) with CoCl3·6NH3, all three
chloride ions got converted to AgCl (silver chloride). However, when AgNO3 was mixed
with CoCl3·5NH3, two moles of AgCl were formed.

Further, on mixing CoCl3·4NH3 with AgNO3, one mole of AgCL was formed. Based on this
observation, the following Werner’s theory was postulated:

Postulates of Werner’s Theory

 • The central metal atom in the coordination compound exhibits two types of
valency, namely, primary and secondary linkages or valencies.
• Primary linkages are ionizable and are satisfied by the negative ions.
• Secondary linkages are non-ionizable. These are satisfied by negative ions.
Also, the secondary valence is fixed for any metal and is equal to its
coordination number.
• The ions bounded by the secondary linkages to the metal exhibit characteristic
spatial arrangements corresponding to different coordination numbers.

Magnetic Properties of Complexes

1. The complex in which a central transition metal ion has unpaired electrons
is paramagnetic.
2. The complex in which a central transition metal ion has no unpaired electrons
is diamagnetic.
3. The magnetic moment of a complex is calculated by the spin only formula.

M = √[n(n+2)] BM

BM = Bohr Magneton

The magnetic moment of complex compounds depends upon the following:

• Type of hybridization.
• The oxidation state of central transition metal ion.
• The number of unpaired electrons.

Applications of Coordination Compounds

The characteristic properties possessed by coordination compounds that were
discussed in the previous subsection make them extremely useful in various
processes and industries. Some of the applications of coordination compounds are
given below.

• The colour of the coordination compounds containing transition metals causes

them to be extensively used in industries for the colouration of materials. They
find applications in the dye and pigment industries.
• Some complex compounds containing cyanide as a ligand are used in the
process of electroplating. These compounds are also very useful in
photography.
 • Coordination complexes are very useful in the extraction of many metals from
their ores. For example, nickel and cobalt can be extracted from their ores via
hydro-metallurgical processes involving ions of coordination compounds.

Applications in Laboratory

• Ni+2 is estimated using a complexing agent Dimethylglyoxime (DMG). The

hardness of water is estimated using complexes of Ca++ and Mg++ with ED↑A
• In Medicine: Cisplatin is used in the treatment of cancer.
• In Photography: Developing of the film involves complex formation.
• In Metallurgy: In the extraction of gold and silver by the Mac Arthur Forest
Process involves a complex of cyanide ions.