CORDINATION COMPOUNDS

INTRODUCTION
(a) The concept of coordination compounds arises from the complex formation tendency of
transition elements.
(b) These compounds play a vital role in our lives. Haemoglobin of blood and chlorophyll of
plants are also coordination compounds of Fe, Mg respectively.

TYPE OF COMPOUNDS
Molecular or Addition Compounds

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(a) When two or more simple salts are chemically combined together in fixed proportion by
weight the molecular or addition compounds are formed.
(b) Some common examples are as follows.

(c) Depending upon the behavior in an aqueous solution they are of two types
(i) Double salt (ii) Coordination or complex compounds.
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(I) Double Salt
The addition compounds which loose their identity in aq. solution and get completely ionised in
water.
Ex. (i) K2SO4.Al2(SO4)3.24H2O (Potash Alum)
(ii) FeSO4(NH4)2SO4.6H2O (Mohr's salt)
(iii) KCl.MgCl2.6H2O (Carnallite)
(II) Coordination or Complex Compounds
A

(a) Those molecular or addition compounds which retain their identity in aq. solution or loose
the identity of constituents are called complex salt.
(b) Complexes retain their identity in aqueous solution. i.e., they do not dissociate into separate
ion.
B

(c) On the basis of type of ligands complex compounds are divided as follows:
(i) Homoleptic complexes :
Complex in which all the ligands are identical is called homoleptic complex.
+2
Ex. [Co(NH3)6]
(ii) Heteroleptic complexes :
Complex in which all the ligands are not identical is known as heteroleptic complex.
+1
Ex. [Fe(en)2Cl2]

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TERMINOLOGY OF COMPLEX COMPOUNDS

(a) Complex Ion/Coordination sphere
• An aggregate of metal ion with anions, cation or neutral molecules is called as complex
ion.
• It is a non ionisable part of complex compoud.
(b) Central Metal Ion
(i) The metal ion which forms complex ion in combination with anions, cation or neutral
molecules is called as central metal ion.

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(ii) Central metal ion acts as an electron pair acceptor and forms coordinate bonds with donor
species.
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(iii) Generally belongs to d block because d block elements have tendency to form complex due
to their high charge density and availability of vacant orbitals.
(c) Coordination Number
The total number of coordinate bonds formed by central metal ion with donor species is called as
coordination number of central metal ion.
(d) Ionisation Sphere
The part of complex comound which get ionised is known as ionisation sphere.
A

(e) Oxidation State

It is a number which represents the electrical charge on the central metal atom of a complex ion.
4— 3+
Ex. the oxidation number of Fe, Co and Ni in [Fe(CN)6] , [Co(NH3)6] and Ni(CO)4 is +2, +3
and zero respectively.
B

(f) Charge On the Complex Ion

It is the algebraic sum of the total charge of the donor species and central metal ion.
(g) Ligands
(i) The anions, cation or neutral molecules which combine with central metal ion to form
complex ion are called as ligands.
–
(ii) They act as electron pair donor (Lewis bases) which donate e pair to central metal ion and
form coordinate bonds.
–
(iii) no. of e pair donated by a ligand to central metal ion is equal to its denticity.

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(h) Naming of ligands

(i) o-suffix is used in the name of anionic ligands.
(ii) ium-suffix is used in the name of cationic ligands.
Classification of ligands :
On the basis of denticity:
–
1. Monodentate ligands : Which donate one e pair to the central metal ion.
Neutral monodentate ligands
NH3 ammine
H2O aqua

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NO nitrosyl
Cationic monodentate ligands :
+
NO nitrosylium or nitrosonium
Anionic monodentate ligands :
–
F Fluorido / fluoro
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–
Cl Chlorido / chloro
–
Br bromido / bromo
–
I iodido / iodo
–
OH hydroxido / hydroxo
–
2. Bidentate ligands : Ligands which donates two e pair to the central metal ion.
Ligands having denticity 2 or more than 2 form a stable ring with central metal ion that's why
they are known as chelating ligands.
A

no. of rings = Denticity – 1

NH2 CH2 CH2 NH2 O O

N N M+

M+ O
B

O
M+
Ethylene diamine (en)
dipyridyl(dipy) oxalato(ox) or C2O4
–2

O H
O
H2N CH2 C
CH3 C CH C CH3 CH3 C N
O
O O M+
CH3 C N
M+
+
glycinato(gly)
— M O
(unsymmetrical) acetyl acetonato (acac)— dimethyl glyoximato(dmg)—

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3. Polydentate ligands

CH2 CH2 NH CH2 CH2 CH2– CH2–NH–CH2–CH2–NH–CH2–CH2

H2 N NH2 H2N NH2

+
M M
+

Diethylenetriamine(dien) Triethylenetetraamine (trien)

Tridentate Tetradentate

OOC CH2 CH2 COO

N CH2 CH2 N
OOC CH2 CH2 COO

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4–
Ethylene diaminetetraacetato (EDTA )
Hexadenatate

4. Ambidentate ligand : Ligands which have two different donor atoms but at one time one donor
atom can donate electron pair are called ambidentate ligands.
Ambidentate ligands have same molecular formula but have different donor atom.
(i) M C N cyanido (CN)
M N C isocyanido(NC)
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(ii) M O C N cyanato / cyanato-O
M N C O isocyanato / cyanato-N
(iii) M S C N Thiocyanato / Thiocyanato-S
M N C S Isothiocyanato/thiocyanato-N
(iv) M O N O Nitrito / Nitrito-O
O
M N Nitro / Nitrito-N
O
IUPAC NOMENCLATURE OF COORDINATION COMPOUNDS
A

The present system of nomenclature derived from the suggestions of Alfred Werner and
recommended by the Inorganic Nomenclature Committee of the I.U.P.A.C. The main rules of
naming of complexes are -
(a) Like simple salts, the positive part of the coordination compound is named first.
Ex. K4[Fe(CN)6 ] the naming of this complex starts with Potassium.
(b) In the naming of complex ion, ligands are to be named before the naming of central metal
B

ion.
(c) If no. of ligands are more than one then their presence is indicated by prefixes like di, tri,
tetra etc. but in case of polydentate ligands different prefixes such as bis, tris are used.
(d) When more than one type of ligand is present in the complex, then the ligands are named in
the alphabetical order.
(e) If the complex is neutral or cationic then the central metal ion is to be named as it is.
If the complex is anionic complex then the name of central metal ion ends in 'ate'
(f) After the naming of central metal ion, oxidation state of central metal ion is written in
Roman numeral.

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The naming of some of the complexes is done as follows – (as per IUPAC)

Complex Compounds IUPAC Name

(i) K4[Fe(CN)6] Potassium hexacyanidoferrate (II)

(ii) K2[HgI4] Potassium tetraiodidomercurate (II)

(iii) [Co (NH3)6] Cl3 Hexamminecobalt (III) chloride

(iv) [Cr(H2O)4Cl2] Cl Tetraaquadichlorochromium (III) chloride

(v) [Pt(NH3)2Cl4] Diammine tetrachloroplatinum (IV)

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(vi) [Co(NH3)3 Cl3] Triamminetrichlorocobalt (III)

(vii) K3[Co(NO2)6 ] Potassium hexanitrocobaltate (III)

(viii) Na2[Fe(CN)5 NO] Sodium pentacyanonitrosoniumferrate (II)

–2
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(ix) [NiCl4] Tetrachloronickelate (II) ion
+2
(x) [Ru(NH3)5Cl] Pentamminechlororuthenium (III) ion

(xi) [Fe(en)3]Cl3 Tris (ethylenediamine) iron (III) chloride

(xii) [Ni (Gly)2 ] Bis (glycinato) nickel (II)

(g) If coordination compound contains 2 coordination spheres then both spheres should have

opposite charges. Name of cationic part is written first following the name of anionic
A

sphere according to the general IUPAC rule.

+2 –2
eg. [Pt(NH3)4] [PtCl4]

Tetraammineplatinum (IV) tetrachloroplatinate (II)

B

(h) If in a complex compound bridging ligands is present then µ – prefix is used before its

name.
NH2
(en)2CO CO(en)2 (SO 4)2
OH
bis (ethylene diamine) cobalt (III) – µ–amido–µ–hydroxo bis (ethylenediamine) cobalt (III)

sulphate

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BONDING IN COORDINATION COMPOUNDS

(A) WERNER'S THEORY
This was postulated by Alfred Werner in 1893. The postulates of Werner's theory of complexes
are –
According to Werner central metal atom in a complex compound have 2 types of valencies :
Primary valencies Secondary valencies
(i) Equal to oxidation state of CMA (i) Equal to coordination number of CMA
(ii) Satisfied by anions (ii) satisfied by ligands
(iii) Non directional (iii) Directional
(iv) Ionisable (iv) Non-ionisable
(v) not helpful in geometry prediction of (v) helpful in geometry prediction of

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complex ion complex ion
Experimental evidence of werner's theory
(a) Precipitation of primary valencies on the addition of suitable reagent. In a series of
compounds of cobalt (III) chloride with ammonia, it was found that some of the chloride
ions could be precipitated as AgCl on adding silver nitrate solution but some remained in
solution.
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AgNO3
1 mole CoCl3 6NH3 3 moles of AgCl
white ppt
hence CoCl3 6NH3 is formulated as [Co(NH3)6]Cl3
+3 –
Which ionises as [Co(NH3)6] 3Cl (4 mole ions)
AgNO3
1 mole CoCl3 5NH3 2 moles of AgCl
hence CoCl3 5NH3 is formulated as [Co(NH3)5Cl] Cl2
A

+2 –
Which ionises as [Co(NH3)5Cl] 2Cl (3 mole ions)
AgNO3
1 mole CoCl3 4NH3 1 moles of AgCl
hence CoCl3 4NH3 is formulated as [Co(NH3)4Cl2] Cl
+ –
Which ionises as [Co(NH3)4Cl2] Cl (2 mole ions)
B

(b) Electrical conductance of complexes

More the number of ions provided in aqueous solution greater will be electrical
conductance of the complex in aqueous solution.
eg. order of electrical conductance is
CoCl3 6NH3 > CoCl3 5NH3 > CoCl3 4NH3
–
Effective atomic number (EAN) – Total no. of e associated with central metal ion in a complex
is equal to effective atomic number.

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(B) VALENCE BOND THEORY

This theory was mainly developed by Linus Pauling. The main features of this theory are -
(a) Metal ion when it forms a complex compound undergoes formation of coordinate bond.
(b) During this bond formation, the metal ion acts as electron pair acceptor. For this the metal
ion provides vacant orbitals according to its coordination number.
3+ +3
(c) Ex. In the formation of [Fe(NH3 )6 ] , Fe ion provides six vacant orbitals.
2+ +2
In [Cu(NH3 )4 ] , Cu ion provides four vacant orbitals.

(d) These vacant orbitals undergo hybridisation before bond formation with ligands.

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(e) The vacant hybrid orbitals of metal ion get overlapped with orbitals of ligands containing
lone pair of electrons.
–
(f) If in a complex strong ligand is present then it will cause pairing of unpaired e in (n–1)d

orbitals of central metal ion and if (n–1)d orbitals are involved in hybridisation then inner
orbital complex is formed.
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–
(g) If in the complex weak ligand is present then there will be no pairing of unapaired e in

(n–1)d orbitals and if nd orbitals are involved in hybridisation, outer orbital complex is
formed.
–
(h) If unpaired e is present in the complex then it will be paramagnetic otherwise it will be

diamagnetic.
Applications of valence bond Theory
A

(a) 6-coordinated complexes :

3+
[Co(NH3 )6 ]
– 7 2 +3 6
e configuration of 27Co = [Ar] 3d 4s So, Co = [Ar] 3d 4s° 4p° 4d°
B

3+
Co

Due to presence of strong ligand unpaired electrons get paired up so metal ion provides vacant
'3d' orbitals for hybridisation.

3d 4s 4p 4d
2 3
d sp hybridisation

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This is a diamagnetic complex.

As inner 'd' orbitals are involved in hybridisation, hence it is an inner orbital complex.
3–
[CoF6]
– 7 2 +3 6 0 0 0
e configuration of Co27 = [Ar] 3d 4s Co = [Ar] 3d 4s 4p 4d
3+
Co ion
– –
F is a weak ligand, so unpaired e do not get paired up and vacant 4d orbitals involved in

hybridisation.

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This is a paramagnetic complex.
The outer 'd' orbitals are involved in hybridisation, hence it is an outer orbital complex.
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(b) 4-coordinated complexes :
2–
[NiCl4]
– 8 2
e configuration of 28Ni = [Ar] 3d 4s
+2 8 0 0
Ni = [Ar] 3d 4s 4p
–
There will be no pairing of unpaired e in 3d orbitals.
A

2—
[NiCl4] has tetrahedral geometry.
It is a paramagnetic complex.
2–
B

[Ni (CN)4]
8 2 +2 8 0 0
28
Ni = [Ar] 3d 4s Ni = [Ar] 3d 4s 4s
– –
CN is a strong ligand so unpaired e in 3d orbitals get paired up

3d 4s 4p
2
dsp hybridisation
2–
[Ni(CN)4] has square planer geometry and diamganetic in nature.

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This complex is an inner orbital complex

2+
[Zn(NH3)4]
2 10
Zn = [Ar] 4s 3d
+2 10 0 0
Zn = [Ar] 3d 4s 4p
+2 10
Zn has d configuration

So there is no possibility of pairing

3d 4s 4p

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sp3
3
Because the complex is formed by sp hybridisation, hence it has tetrahedral geometry.
Since all electrons are paired, hence it is diamagnetic
8 2
[Ni(CO)4] Ni = [Ar] 3d 4s 4p°
–
CO is a strong ligand so unpaired e in (n–1)d orbitals get paired up.
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Ni =
3d 4s 4p
3
sp hybridisation
3
Complex has sp hybridisation
It has tetrahedral geometry.
–
It is diamagnetic complex as unpaired e is absent.
A

2+
[Cu(NH3)4]
1 10 +2 9 0 0
29
Cu = [Ar] 4s 3d Cu = [Ar] 3d 4s 4p

NH3 is a strong ligand so after rearrangement

B

2
Complex has dsp hybridisation
It is inner orbital complex
It has square planer geometry
It is paramagnetic

4s 4p
2
dsp

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(C) Crystal field theory

Crystal Field Theory : This is a model of electronic structure of transition-metal complexes that
considers how the energies of the d-orbitals of a metal ion are affected by the electric field of the
ligand. According to this theory.
(a) Central metal ion is considered as a positive point charge, anionic ligand as a negative
point charge, neutral ligand as a point dipole and attraction between metal ion and ligand is
electrostatic in nature.
(b) In the electric field of ligands, the five d orbitals of the metal atom no longer have exactly
same energy while they are splitted into different energy levels. Splitting of five degenerate

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d-orbitals of the metal ion into sets of orbitals having different energies is called crystal
field splitting.
(c) The extent of splitting of metal d-orbitals depends upon the nature and number of ligands
surrounding it and the charge on the central metal ion.
(d) The extent of splitting of metal d-orbitals determines the magnetic and spectroscopic
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properties of the complexes.
SPLITTING IN OCTAHEDRAL COMPLEXES
In a octahedral complex, the co-ordination number is 6. The metal ion is at the centre and the
ligands occupy the six corners of the octahedron as shown in figure.
We know that two orbitals, d x 2 y2
and d z2 are oriented along the axis while the remaining three

orbitals, viz., dxy, dyz and dzx are oriented in between the axis.
Z
A

L L L
X
L
B

Y L

The two orbtials d x 2 y2

and d z2 are designated as eg orbitals while the three orbitals dxy, dyz and

dzx are designated as t2g orbitals. As the six ligands approach the central ion along the axis hence

eg orbitals, is repelled more by the ligand than the t2g orbitals.

In other words, the energy of the eg orbitals increases much more than the energy of the t2g
orbitals.

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Thus, in octahedral complexes, the five d-orbitals split up into two sets : one set consisting
of two orbitals ( d x2 -y2 and d z2 ) of higher energy (eg orbitals) and the other set consisting of

three orbitals (dxy, dyz and dzx) of lower energy (t2g orbitals).

eg
0.6
= crystal field splitting
–0.4 energy of octahedral complex
State II t2g

State III

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State I
Splitting in tetrahedral complex
The co-ordination number for tetrahedral complexes is 4. The tetrahedral arrangement of four
ligands surrounding a metal ion may be visualized by placing ligands at the alternate corners of a
cube, as shown in figure.
Z
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L
L
M+ X
L
Y L
Tetrahedral arrangement
of four lignads
It can be shown that in a tetrahedral structure, none of the d-orbitals points exactly towards the
ligands.
A

When ligand approaches it is more close dxy, dyz, dxz in comparision of dx2–y2 and dz2 because dxy,
dyz, dzx are between the axis and dz2 and dx2–y2 are along the axis. So dxy, dyz, dzx feels more
repulsion as compare to dz2 and dx2 – y2.
Thus, the d orbitals are also splitted into two groups but in a reverse order of octahedral complex.
B

The three orbitals, dxy, dyz and dxz, designated are now have higher energy than the two orbitals
d x2 y2
and d z2 .

t2
0.4 t

State II –0.6
t
t
= Spitting energy of tetrahedral complex
e
State I State III

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Calculation of crystal field stablizing energy (CFSE)

For octahedral complex CFSE = –0.4 n t 2 g 0.6 n eg 0 + Pairing energy (P.E.)

where n t 2 g = number of electron in t2g orbitals

neg = number of electron in eg. orbitals

0
= crystal field splitting energy

APPLICATION OF CRYSTAL FIELD THEORY

Applications of C.F.T are

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(i) To explain weather complex is high spin or low spin complex.
(ii) To explain colour property
(iii) To explain stability of complex

(II) COLOUR PROPERTY OF COMPLEX COMPOUNDS :

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Reason for colour in complexes is due to d-d-transition

1
eg
0
eg
energy

d-d transition

t2g1 t2g0
ground state excited state
A

P V I
R B
Complentary colour wheel For example complementry colour of red is blue
O BG
green.
Y G
YG
B

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