Inorganic Chemistry

Coordination
Compounds

OM PANDEY
IIT DELHI
 Addition Compounds
The combination of two or more stable compounds

K2SO4 + Al2(SO4)3 + 24H2O Fe(CN)2 + 4 KCN

Double Salts Coordination Compounds

Addition compound , which Addition compounds , which

lose their identity in aq. don’t lose their identity in aq.
solution. solution.
Co-ordination Compounds

K4  Fe ( CN)6 
 Ligands
The ligands are the ions or molecules bound to the central atom/ion in the
coordination entity.

[ Co(NH3)6]3+
 Denticity
The no. of coordinate bonds that a ligand can form with Metal.

[ Co(NH3)6]3+

[ Co(en)3]3+
 Monodentate Ligand
Only one donation is accepted from the ligand

ite ito NO2–

ide ido OH–

ate ato NO3–

Ligands Name
H2O Aquo

CO Carbonyl

NO Nitrosyl

NH3 Ammine

F– Fluorido

Cl– Chlorido

Br – Bromido

I– Iodido

NO+ Nitrosonium
Ligands Name
NH2− Amido
CH3 – NH2 Methylamine
CH3COO– Acetato
– OH
Hydroxo
H– Hydrido
CN – Cyano / cyanido
Ligands Name
N3– Nitrido

N3− Azido

C2O24− Oxalato

SO24− Sulphato

SO3− Sulphito

S2– Sulphido
 Bidentate
Two donations are accepted from the ligand.

O O O O
C—C C—
C
–O O– –O O– –O NH2

Carbonato Oxalato Glycinato

 Chelation

[ Co(NH3)6]3+
Co

[ Co(en)3]3+ Co

Chelates are generally more stable than non chelate complexes.

 EDTA
Polydentate Ligand
 Flexidentate Ligand

A polydentate ligand with different denticity in different coordination compounds

SO42–
 Ambidentate Ligand
Ligands that have more than one kind of donor sites

NO2−

CN−

SCN−

OCN–
 Co-ordination Number
The no. of ligand donor atoms to which the metal is directly bonded.

[PtCl6]2–
Pt

[Co(en)3]2+

Co
 Co-ordination Polyhedron

The spatial arrangement of the ligand atoms

[Ni(CO)4] Ni

[Co(NH3)6]+3 Co
 Complexes

Homoleptic Complex Heteroleptic Complex

Metal is bound to only one kind of A metal is bound to more than one
donor groups kind of donor groups

[ Co(NH3)6]3+ [Co(NH3)3Cl3]+
 IUPAC name of a Complex
Cation is named first, followed by anion. [Cr(H2O)4Cl2] Cl

K3 [Fe(CN)6] [Ag(NH3)2] [Ag(CN)2]

In naming of complex ion, the ligands are named first in the alphabetical order.

Use prefix di, tri, tetra for multiple ligands of same kind.

(H2O)4 tetraaqua

(CN)6 hexacyano

(NH3)3 triammine
If ligand’s name already contains any of these prefix, then we use bis, tris,
tetrakis instead of di, tri & tetra and name of ligand is enclosed in parenthesis.

(en)2 bis (ethylenediamine)

If the complex ion is a cation, the metal is named same as the element.

[Cr(H2O)4Cl2]Cl

If the complex is anion, name of metal ends with the suffix –ate.

Cr Chromium Chromate
Metal Name in Cationic part Name in Anionic part

Pt platinium platinate

Co cobalt cobaltate

Ni nickel nickelate

Zn zinc zincate

Pb lead plumbate

Ag silver argentate

Au gold aurate

Sn tin stannate

Fe iron ferrate
 K3[Fe(CN)6]

Ni(CO)4

[ Ag(NH3)2 ] [ Ag(CN)2 ]
[Pt(NH3)2Cl4] Diammineterachlorido platinum(IV)

[NiCl2(pph3)2] Dichloridobis(triphenylphosphine) nickel (II)

[Cr(NH3)3(H2O)3]Cl3 Triamminetriaquachromium(III) chloride

[Pt(NH3)5Cl]Br3 Pentaammine chlorido platinum(IV) bromide

 Werner’s Theory
CoCl3.6NH3 CoCl3.5NH3 CoCl3.4NH3
 Werner’s Theory
CoCl3.6NH3 CoCl3.5NH3 CoCl3.4NH3

Conductivity
 Valences of Metal
Primary Valency Secondary Valency

Ionisable Valency

Non-directional

Modern
Representation

NH3
NH3 NH3
Cl ………… Co+3 …………Cl
CoCl3 . 6NH3 H3N NH3
NH3

Cl
Werner Complex Modern Notation Ionisation Secondary Primary Val.

CoCl3 . 6NH3

CoCl3 . 5NH3

CoCl3 . 4NH3
 Valence Bond Theory

Covalent molecule Co-ordination complex

Hybridisation

Vacant orbitals
Half-filled orbitals
Fully-filled orbitals
Coordination Number Type of Hybridisation Structure

6
It is usually possible to predict the geometry of a complex from the knowledge
of its magnetic behaviour on the basis of VBT.

Magnetic moment  = n (n + 2)

n=

Paramagnetic complex =

Diamagnetic complex =
[Co(NH3)6]3+ Diamagnetic
[FeF6]3– Paramagnetic
 d-line for Hybridisation

d0 d1 d2 d3 d4 d5 d6 d7 d8 d9 d10
[Mn(CN)6]3– : Magnetic moment of 2 electrons

[MnCl6]3– : Magnetic moment of 4 electrons

[NiCl4]2– Paramagnetic
Ni(CO)4 Diamagnetic
[Ni(CN)4]2- Diamagnetic
 Crystal field Theory
Electrostatic model which consider the metal – ligand bond to be ionic.

Ligands Point charges in case of anions

Dipoles in case of neutral molecules

d-Orbital
Crystal field splitting L

L L
M
M M
L L
L

Energy
 eg eg

d1 d2

t2g t2g

eg

d3

t2g
 d4

0 0’

If 0 < P If 0 > P

Configuration = Configuration =

Ligands for which 0 < P are know as Ligands for which 0 > P are known
weak field ligand. as strong field ligand.
 Spectrochemical Series
Series of ligands in the order of increasing field strength.
Halogen donors Oxygen donors Nitrogen donors Carbon donors
I– Br – SCN– Cl– S2– F– OH– C2O42– H2O NCS– EDTA4– NH3 en CN – CO

3d Series : 4d / 5d Series :
Metal (+2) : I– → en Metal (+2)
Metal (+3) : I– → H2O Metal (+3)
Metal (+4) : Metal (+4)

Co+3 [ H2O/O2– / OH– / Ox2– ]

 o depends on
I– Br – SCN– Cl– S2– F– OH– C2O42– H2O NCS– EDTA4– NH3 en CN – CO

Series

Charge

Ligands

Complex kJ mol–1
[ Co(NH3)6 ]3+ 296

[ Rh(NH3)6 ]3+ 406

[ Ir(NH3)6 ]3+ 490

 o depends on
[Fe(CN)6]3– [FeF6]3–
 Crystal Field splitting in tetrahedral complex
In tetrahedral coordination entity formation the d orbital splitting is inverted and
is smaller as compared to the octahedral field splitting.

Energy
 t2 t2

d1 d2

e e

t2 t2

d3 d4

e e
 Colour in Co-ordination Compounds

Ti(H2O6)3+

When light of certain frequency falls on the complex, it absorbs light from visible
range for transition of electrons from lower d-energy level to higher d energy
level. This transition is called d-d transition of electron.

Colour of the compound is the complementary colour of absorbed light.

[ Co(NH3)6 ]3+ [ Co(NH3)6 ]2+

[Fe(CN)6]3– [FeF6]3–
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