E- Content- B.Sc.

II Inorganic chemistry
Topic
BASIC CONCEPT OF COORDINATION COMPOUND

DR PREM YADAV

Assistant Professor
Department of Chemistry
N.S.P.S. Government PG College
Magarah, Mirzapur (U.P.) INDIA
e.mail: prem77yadav@gmail.com
CONTENTS PART:A

History of coordination compounds

Definition
Terms use in Coordination Compound
Type of Ligand
Examples of ligand
Nomenclature
Effective atomic Number(EAN)
Werner’s theory
 History of coordination compounds

The first scientifically recorded observation of a completely inorganic

coordination compound is German chemist, physician, and alchemist Andreas
Libavius’s description in 1597 of the blue colour (due to [Cu(NH3)4]2+) formed
when lime water containing sal ammoniac (NH4Cl) comes into contact with brass.
In 18th century, another example of a coordination compound is the
substance Prussian blue, with formula KFe[Fe(CN)6], which has been used as an
artist’s pigment. Another early example of the preparation of a coordination
compound is the use in 1760 of a sparingly soluble compound, potassium
hexachloroplatinate(2−), K2[PtCl6], to refine the element platinum.
The exact date of preparation of the first coordination compound is not
exactly known.
The discovery of Hexa ammine cobalt (III) chloride [Co(NH3)6]Cl3 by the
French chemist B.M. Tassaert in 1798, is generally regarded as the beginning of
coordination chemistry
Cont….

In the 19th century, as more complexes were discovered, a number of

theories were proposed to account for their formation and properties. The most
successful and widely accepted of these theories was the so-called chain theory
(1869) of the Swedish chemist Christian Wilhelm Blomstrand
Chain Theory was modified and developed by the Danish chemist Sophus
Mads Jørgensen. Jørgensen’s extensive preparations of numerous complexes
provided the experimental foundation not only for the Blomstrand-Jørgensen
chain theory but for Alsatian-born Swiss chemist Alfred Werner’s coordination
theory (1893) as well.

Werner was the first inorganic chemist to be awarded the noble prize in
chemistry (1913) Alfred Werner Swiss chemist put forward a theory to explain the
formation of complex compound. It was the first successful explanation, become
famous as the coordination theory of complex compounds, which is also known as
Werner’s theory
DEFINITION
Coordination compounds are species in which a central
metal ion (or atom) is attached to a group of
surrounding molecules or ions by coordinate covalent
bonds
• Surrounding groups are called Ligands
• Central metal is a Lewis acid.
• Ligand is a Lewis base.

Coordination compounds are those molecular

compounds which retain their identities when dissolved in
water or any solvent.

EXAMPLE:

K4[Fe(CN)6] K2[PtCl4] [Co(en)2Cl2]Cl

Pt(NH3)2Cl2
TERMS USE IN COORDINATION COMPOUND

Central ion or centre of coordination: Cation in which one or

more neutral molecules or anion are attached
Coordination Number: The number of donor atoms bound to
the central atom or ion
Oxidation Number: represents the electric charge on the central
metal atom
Coordination sphere: ligands and metal combine to form the
coordination sphere
Charge of a complex: Sum of the charges on
central metal and ligands
Ligand :The Lewis bases that bind (coordinate)
to the metal atom or ion are called ligands
Diagrammatically……
 Type of LIGAND

• Monodentate ligands bond using the electron pairs of a single atom.

• Bidentate ligands bond using the electron pairs of two atoms.

• Polydentate ligands bond using the electron pairs of many atoms.

This group includes Tridentate, Tetradentate, Pentadentate, Hexadentate etc.

•Ambidentate Ligands two or more donor atoms but in forming

complexes only one donor atoms is attached to the metal ion at a given time.
 Nomenclature of Coordination Compounds

The system of naming coordination complexes is in some ways similar to and in

other ways different from naming simple inorganic salts. The rules for nomenclature
are:
• Name the cation first and anion second.
• Within a complex ion, the ligands are named alphabetical order.
• Numbering prefixes (e.g. di, tri, …) are not used in alphabetizing.
• Anionic ligands end in the letter “-o,” while neutral molecules (with a few
exceptions) retain their names.
• The prefixes di-, tri-, tetra-, penta- and hexa- are used to indicate the number of each
ligand. If the ligand name includes such a prefix, the ligand name should be placed in
parentheses and preceded by bis- (2), tris- (3), tetrakis- (4), pentakis- (5), and hexakis-
(6).
• If a complex is an anion, it should end in “-ate.”
• Place the metal oxidation number in parentheses as a Roman numeral
Examples

 [Cr(H2O)5Cl]SO4 pentaaaquachlorochromium(III) sulfate

 [Cr(H2O)5Cl]2+ pentaaquachlorochromium(III) ion
 [Cr(NH3)3Cl3] triamminetrichlorochromium(III)
 K2[PtCl4] potassium tetrachloroplatinate(II)
 [Co(en)2Cl2]Cl dichlorobis(ethylenediamine)cobalt(III) chloride
 Pt(NH3)2Cl2 diamminedichloroplatinum(II)
 K2[PtCl4] potassium tetrachloroplatinate(II)
 [PtCl4]2– tetrachloroplatinate(II) ion
 [Co(en)2Cl2]Cl dichlorobis(ethylenediamine)cobalt(III) chloride
 [Cu(NH3)4]SO4 tetraamminecopper(II)sulfate
 K4[Fe(CN)6] potassium hexacyanoferrate(II)
 [Cr(NH3)6][IrCl6] hexaamminechromium(III) hexachloroiridate(III)
 [Cr(H2O)2BrClFI]– diaquabromochlorofluoroiodochromate(III) ion
EFFECTIVE ATOMIC NUMBER(EAN)

 Effective atomic number (EAN), number that represents the total number of electrons
surrounding the nucleus of a metal atom in a metal complex.

 The tendency to attain an inert gas configuration is a significant factor.

 It is composed of the metal atom's electrons and the bonding electrons from the
surrounding electron-donating atoms and molecules.

EAN = Atomic number of the metal +(Number of ligands X electrons donated by each ligand) - positive oxidation
state of the metal

For example,
Fe ⇒ atomic number is 26
and forming a complex, [Fe(CN)6]4–
the number of electrons lost = 2
the number of electrons gained = 12
So, EAN = 36

It is used to check the stability of metal in coordination complex.

 WERNER’S THEORY

Alfred Werner Swiss Chemist put forward a theory to

explain the formation and structure of complex
compounds which is later termed as Werner’s Theory of
Coordinate Compounds.
Due to this theory he is awarded by Nobel Prize and he
is also called the ‘Father of Coordination Chemistry’
 Postulates of Werner’s Theory

The important postulates of Werner’s theory are as follows:

 In coordination compounds, the central metal or metal atoms exhibit
two types of valency-
primary valency and the secondary valency
 The primary valency corresponds to oxidation state and the secondary
valency corresponds to coordinate number.
 Every metal atom has a fixed number of secondary valencies, i.e It has
fixed coordinate number.
 The metal atom tends to satisfy its both primary and secondary
valancies.
 Primary valency is satisfied by negative ion whereas secondary
valancies are satisfied by negative ion or by neutral molecules.
 The secondary valancies are always directed towards fixed position in
space and this cause definite geometry of the coordinate compound.
 The secondary valency thus determines the stereochemistry of the
complex ion. On the other hand, the primary valency is non-directional.
THANKS
References:
1. Principle of Inorganic
Chemistry by Puri,
Sharma & Kallia
2. Concise of Inorganic
Chemistry by J.D.Lee