Module 2.

Coordination number; chelate effects

A complex is the result of an interaction between a metal ion and a certain

number of ligands. The qualities of the metal ion and the ligands ultimately
dictate the coordination number of the metal ion and the geometry i.e. the
stereo chemistry of the complex.

It is not always possible to predict the coordination number of a metal ion

and the resulting stereochemistry of the complex. However certain broad
features can be noted as follows.

1. The coordination number will tend to be as large as possible since the

attraction between the metal ion and the dipolar molecules or the anions
are involved in complex formation.
2. The arrangement of the coordination ligands must be such that it
minimizes the electrostatic repulsions between the ligands.

An ML2 type complex should be linear as such geometry maximizes

ligand distance and hence minimizes the repulsion between the two L -
groups.

LML

Similarly an ML3 complex should have three ligands at the vertices of an

equilateral triangle.
 For a coordination number 4 (ML4 complex), the four ligands (L groups)
may be placed at the corners of a regular tetrahedron or at the corners
of a square plane. In both the stereo chemistries repulsive forces
between the ligands are maximum.

Likewise the coordination number five permits two stereo chemistries.

They are:

i. Square pyramid
ii. Trigonal bypyramid.

An octahedron, a hexagon or a trigonal prism satisfies a coordination

number six. In actual practice octahedron is the preferred geometry.

There is no fixed coordination number or stereo chemistry for any given

ion. A particular stereo chemistry may be enforced by

a. The donor strength of the ligand.

b. The steric requirements of the ligands
c. The size of the central metal ion or atom. And
d. The charge on the central metal . etc.

Examples of different complexes showing different coordination

numbers and stereo chemistries.

Hybridization
Coordi Stereochemist
Structure Examples of the central
nation ry
metal ion or
 atom .
2
Linear sp

Distorted
3 equilateral sp2
triangle sp2

Square planar
4 dsp2 (or) sp2d
(ML4)

Tetrahedral
4 sp3
(ML4)

Octahedral
6 sp3d2 (or) d2sp3
(ML4)
DMG = Dimethyl glyoximate ion; en = enthylene diamine

PPh3= Triphenyl phospine

PPh3O= triphenyl phosphine oxide

a. Trigonal bypyramidal (ML 5)

b. Square pyramidal (ML5)

Chelates and chelating effects:

In the formation of certain complexes, a ligand may satisfy two or more

coordinating sites on the central metal atom or ion. On coordination, such
ligands produce closed rings or cyclic structures containing the metal.
These complexes thus formed are known as chelates. (Greek: Chele =
claw). And the bidentate or polydentate ligands that form the chelates are
known as chelating agents or chelating ligands.

Example:

Hemoglobin and chlorophyll are well known chelates. Ca+2 and Mg+2 ions
produce chelates with EDTA. (i.e. ethylene diamine tetra acetic acid).
Following are some of the characteristics of chelates.
i. Complexes with chelate rings are more stable than those without the
chelate rings. The increase in the stability a complex due to the
formation of a chelate is known as chelating effect.
ii. Chelates containing 5 or 6 membered rings are comparatively more
stable than compounds without chelate rings. More the number of
chelate rings, greater the stability of the complex compound.

Example:

[Cu (en)2]+2 is more stable than [Cu (NH3)4]+2

[Cu (en)2]+2 is less stable than [Fe (EDTA)].
iii. Ligands with larger groups form unstable chelates compared to those
with smaller groups. That is due to steric hindrance.
iv. Dissociation of chelate compounds involves the cleavage of more
number of ions than compounds that do not contain chelate rings.
v. Chelation always results in an increase in the number of molecules or
species present in the system.

Example:

[Cn (NH3)4]+2 + 2 (en) [Cu (en)2]+2 + 4 NH3

Total no of species = 3 Total no of species = 5

Applications of chelate compounds:

Now -a- days chelate compounds are utilized in a number of fields. A few of
them are given here.

i. In medicine:
 Heavy metals like lead; mercury iron; copper; nickel; and chromium
are toxic. They form complexes hindering the normal metabolism.
They are eliminated by a suitable chelating agent.

Example:

Dermatitis caused by Cr and Ni is treated with EDTA cream.

Pb and Cu poisoning is treated with Ca EDTA complex. Pb and Cu

form chelates with EDTA and are eliminated.

ii. In softening of hard water:

To prevent scales formation in boilers, calgon (chemical name is

sodium hexa metaphosphate) is added. Then Ca+2 and Mg+2 ions,
that are responsible for hardness of water, are eliminated as complex
compounds.

Ca+2 + [Na4 (PO3)6]2 Ca[Na4 (PO3)6] or [Ca2 (PO3)6]2

iii. In analytical chemistry:-

Chelate formation is used in the estimation of the hardness of water.

Ca+2 and Mg+2 ions form complexes with EDTA.

In the quantitative analysis for the detection of Ni, di methyl glyoxime

is used as a sensitive reagent.

iv. Solvent extraction and separation of metal ions through

complexation, can be achieved in the case of metal ions like Iron (III)
and aluminium (III) ions. They form first order complexes with 8-
hydroxyquinoline,(L). 8 Hydroxy quinoline is a very good chelating
 agent for the separation and estimation of the two ions. FeL3 is
formed at pH 2 to 10; and is soluble in chloroform.

AlL3 is formed at higher pH and is not readily soluble in CHCl3

Therefore they can be separated by addition of 8-Hydroxyquinoline

and extracting with CHCl3 .

v. In the presence of EDTA, beryllium may be precipitated with

ammonia in the presence of several metal ions like Al+3; Bi+3; Cr+3;
CO+3; Cu+2; K+3; Pb+2 etc.
vi. Spectrophotometic estimation of trace amounts of metal ions:
Several transition metal ions form complexes with intense colours.
They can be determined by measuring the optical density of the
complex at optimum wavelength.

Ex: Fe(ii) ion forms dark red complexes with dipyridine or

o- phenanthroline at pH 2 to 9; max = 515 m.

Fe(III) ion forms a complex [Fe(SCN)6 ]-3 in 0.05 0.5M HNO3; max =
480m

vii. Use of insoluble inner metallic complexes in gravimetric analysis:

a) Estimation of Ni(II) as a red coloured bis(dimethylglyoximato)
nickel(II).
b) Tris (8-hydroxy quinolinato)Al(III) as yellow coloured ssolsid.
c) Light green coloured bis(quinaldinato)copper(II) or as dull green
coloured bis(salicylaldoximato) copper(II).
Structure of EDTA:

Assignment questions:

1. What are the main features of (i) coordination number and (ii)
stereochemistry of complex compounds?
2. Write a note on chelate compounds.
3. How are chelate compounds useful to the scientist?