Prussian blue is a coordination compound containing both iron (II)

and iron (III) linked together by cyanide ligands (KFe[Fe (CN)6]). It

was discovered in 1704 by Diesbach and gets its name from the
fact that it was used to dye the uniforms of the Prussian army a
deep blue color. It has been used by artists as a pigment in
paintings from the mid-eighteenth century until the early 1900s.
Prussian blue has also been used in cyanotype
photography,blueprints, and blue jeans.
The bright yellow dye aureolin, or cobalt yellow, has been in use
as a pigment since 1831. Its chemical formula is K 3[Co(NO2)6].6H2O.

Alizarin red is an aluminum lake dye derived from the roots of the
madder plant. It was used in both ancient Persia and Egypt, as well
as by the Greeks and the Romans. Alexander the Great might have
once used the dye to make bloody splotches on his soldiers
uniforms in order to encourage the Persians to attack what they
believed was a demoralized army. The French and British military
have also used alizarin on their uniforms. When Paul Revere said
that the redcoats are coming, he was referring to the bright red
color of the uniforms of the colonial British soldiers. Today, the
alizarin red dye is used as a stain in histology.

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The word ligand comes from the Latin ligare, meaning to bind.
Ligands are also called complexing agents.
A coordinate-covalent bond or commonly called coordinate bond,
also sometimes called a dative bond.
we have known that each bond consists of two electrons, therefor
arguably that the coordinate bond is special type of the covalent
bonding
The coordinate bond often represented as (M :L).
A coordination compound is a Lewis acidbase adduct (how?).
Elements in the f-block, the so-called lanthanides and actinides,
have been in the past called inner transition metals. Nowadays,
they are more often referred to as f-block elements.
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6. Coordination Chemistry
Many metal ions form aggregate with Lewis bases which are stable in
solution, such species are known as coordination compounds or complex
compounds. A complex may be positive ion, a negative ion or even
neutral. It depends upon the charge of the metal ion and the donor.
Example,

[Co(NH3)6]+3, O.N.of cobalt is +3 and NH3 is neutral.

[Fe(CH6]4, O.N. of iron is Fe2+ and cyanide ion (CN) is

uninegative

[Cu(H2NCH2OO)2], O.N. of copper is +2 and glycinate ion is

uninegative.

Complex compound are made by chemical species which have independent

existence, such as Co+3, Fe3+, Cu2+, NH3 CN etc. Thus, complexes are chemical
compounds which contain a metal ion, surrounded by Lewis bases and the
aggregate retain its identity in solution. Lewis bases which form complexes are
known as Ligands (G, ligare to bind).

COORDINATION NUMBER
The number of ligands surrounding a metal ion is coordination number of the
metal ion. In case of polydentate ligands the number of coordinating centres
determine coordination number. For example, ethylene diamine, a bidentate
ligand, satisfies two coordination position.
.Most common coordination numbers found are 4 and 6

Table 6.1

Complex Coordination number

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[Ag(NH3)2]+ 2

[Cu(NH3)4]+2 4

[Fe(CN)6]4 6

[CoCl4]2 4

Types of Ligands
Lewis bases which form complexes are known as Ligands (G., ligare to bind).
:They are classified as

1. Monodentate

Ligands which donate one electron pair to Mn+ are called monodentate. Example,
F, Cl, NH3, H2O, HO

2. Bidentate

Those ligands which can donate two electron pairs to M n+, are known as bidentate.
These are most common.

3. Polydentate

These include tri, tetra, penta, hexadentate ligands. One very useful hexadentate
ligand is ethylene diamine tetracetate (EDTA).

Chelates
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Complexs having ring structure are known as chelates. Thus polydentate ligands
form chelates, [Co(en)2 Cl2], [Cr(en)3]3+ [Ni(en)3]2+.

Figure 6.1

This chelate contains five membered ring structures. Chelates are more stable than
non-chelated complexes (i.e., having no ring structure). This is known as Chelate
Effect. Thus, [Ni(en)3]2+ > > > [Ni(NH3)6]2+, inspite of the fact that both complex
contain equal number of Ni N bonds. Metalloenzymes are chelates.

Conditions for complex formation

A complex contains Mn+ acceptor and ligands are electron pair donors. Metal ions
which satisfy the following conditions form complexes easily:

1. Metal ion should have high charge density,

Charge density = Charge/Radius
Thus, small metal ions form complexes easily.
2. Metal ion should have vacant orbitals of comparable energy in the valence shell.

Non-transition metals form a few complexes whereas transition metals

form variety of complexes. The valence orbitals of transition metals can be
recognized as: