Chapter 14

Chemistry of
Coordination Compounds
 Chemistry of
Coordination Compounds
• In earlier chapters - metal ions can function as Lewis acid,
forming covalent bonds with a variety of molecules and
ions (Lewis bases)
e.g. [Fe(H2O)6]3+ , [Ag(NH3)2]+

• Metal compounds of this kind (metals surrounded by

molecules and ions) are called coordination compounds.

• Note: transition metals readily form

coordination compounds.
 The Structure of Complexes

• Species such as [Ag(NH3)2]+ (a central metal ion bonded to

a group of surrounding molecules) - metal complexes or
complexes.

• A complex carries a net electric charge is generally called

a complex ion.

• Compounds that contain complexes are known as

coordination compounds.
• Ligands/complexing agents:
– molecules or ions that surround the metal ion in a
complex.
– Normally either anions or polar molecules.
– Have at least one unshared pair of valence electrons.
– E.g. H2O, NH3, Cl-, CN-

O H N H Cl C N

H H
• The bond between the metal ion and ligand is the result of
their sharing a pair of electrons:
+
H H H
+
Ag (aq) + 2 N H (aq) H N Ag N H (aq)

H H H

• Ligands coordinate to the central metal.

• The central metal and the ligands bound to it constitute the
coordination sphere of the complex.
• In writing the chemical formula for a coordination
compound, square brackets are used to set off the
groups within the coordination sphere from other
parts of the compound.
– E.g. [Cu(NH3)4]SO4 represents a compound
containing [Cu(NH3)4]2+ cation and SO42- anion.
– E.g. Na[Al(OH)4] consists of Na+ cation and
[Al(OH)4]- anion.
• A metal complex - has its own characteristic physical and
chemical properties.  it has different properties than the
metal ion or the ligands from which it is formed.
• E.g. The colour change that occurs when aqueous solutions
of SCN- and Fe3+ are mixed forming [Fe(H2O)5SCN]2+.

• Other e.g.; Ag+ is readily reduced in water:

Ag+(aq) + e-  Ag(s) E = + 0.799 V

But the [Ag(CN)2]- ion is not easily reduced:

[Ag(CN)2]-(aq) + e-  Ag(s) + 2CN-(aq)
E  = -0.31 V
• This is because complexation by CN- ions stabilizes the Ag+
ion.
 Charges and
Coordination Numbers
• The charge of a complex is the sum of the charges on the
central metal and on its surrounding ligands.
• Eg. [Cu(NH3)4]SO4. Since SO4 (sulphate) ion has a 2-
charge, then the complex [Cu(NH3)4] must have a 2+
charge, [Cu(NH3)4]2+.
• The charge of the complex can be used to deduce the
oxidation number of the central metal.

+2 + 4(0) = +2

[Cu(NH3)4]2+
• The atom of the ligand bound directly to the metal is called
the donor atom.
Eg. [Ag(NH3)2]+ - donor atom N
[Al(OH)4]- - donor atom O

• The number of donor atoms attached to a metal is called

the coordination number of the metal.

• Eg. [Ag(NH3)2]+ - coordination no. of Ag = 2

[Cr(H2O)4Cl2]+ - coordination no. of Cr = 6
[Al(OH)4]- - coordination number of Al = 4
 Example
Determine the oxidation number and the coordination number
of each of the following compounds:
1. [Co(NH3)5Cl](NO3)2
Co + 5 NH3 + Cl = 2+ Coordination No. = 6 (5NH3 + 1Cl)
Co + 5 (0) + (-1) = 2+
Co = +3
2. K4[Fe(CN)6]
Fe = +2 Coordination No. = 6 (6 CN)
3. K4[Ni(CN)4]
Ni = 0 Coordination No. = 4 (4 CN)
 Chelates
• NH3, OH-, CN-, H2O, Cl- - monodentate ligands.
– Monodentate ligands possess a single donor atom and
are able to occupy only one site in the coordination
sphere.
• Some ligands have two or more donor atoms that can
simultaneously coordinate to a metal ion, and therefore
occupying two or more coordination sites.
– They are called polydentate ligands
– Polydentate ligands grasp the central metal between
two or more donor atoms -chelating agents. (chelate -
claw)
– Eg. Ethylenediamine
• Ethylenediamine is abbreviated en. H2C C H2
Two nitrogen atoms have unshared
pairs of electrons. These 2 N atoms H2N NH2
simultaneously complexing to the
metal.

N 3+
Co
• The coordination number for Co is 6.

[Co(en)3]3+
• Eg of a polydentate ligand:
Ethylenediaminetetraacetate (EDTA) ion.
Has six donor atoms.

4-
O O

O C CH2 H2C C O
N CH2 H2C N
O C CH2 H2C C O

O O
 Some common ligands

• Bromide, Br- monodentate

• Chloride, Cl- monodentate
• Cyanide, CN- monodentate
• Hydroxide, OH- monodentate
• Ammonia, NH3 monodentate
• Ethylenediamine, en bidentate
• Pyridine, C5H5N monodentate
• Water, H2O monodentate
• EDTA polydentate
The End