VELAMMAL BODHI CAMPUS, PANCHETTI.

COORDINATION COMPOUNDS

 The compounds in which metal atoms are bound to a number of ions or neutral
molecules through coordinate covalent bond are called coordination compounds.
Postulates of Werner’s theory :
(1) In coordination compounds metals show two types of valences, primary and
secondary valency.
(2) The primary valence is normally ionisable and generally satisfied by negative ions.
(3) The secondary valences are non-ionisable. These are satisfied by neutral
molecules or negative ions. The secondary valence is equal to the coordination
number and is fixed for a metal.
(4) The ions/molecules bound by the secondary valence to the metal have
characteristic spatial arrangements corresponding to different coordination
numbers.
 Generally primary valency is nothing but electrovalency and secondary valency is the
coordination number.
Eg : (1) In the complex compound,
[Co( NH3 )6 ]Cl3
the primary valency is 3
secondary valency is 6
oxidation state is +3
Number of ions obtained per molecule is 4.
(2) In the complex compound
K 4 [ Fe(CN )6 ]
primary valency is 2
secondary valency is 6
coordination number is 6
oxidation state of the metal is +2
Number of ions obtained per molecule is 5.
(3) In the complex compound
[Co( NH3 )3 Cl3 ]
primary valency is 3
secondary valency is 6
coordination number is 6
oxidation state of metal is +3
Number of ions obtained per molecule is 0.
(4) In the complex compound
[ Ni (CO ) 4 ]
primary valency is zero
secondary valency is 4
coordination number is 4
oxidation state of metal is Zero
Number of ions obtained per molecule is ‘0’.
 A complex compound CoCl3. xNH3 gives 2 mole of AgCl precipitate per one mole of
compound. Then
(1) formula of the compound is ..............
(2) Number of ions obtained per molecule is ……………
 As one mole of compound gives two mole of AgCl precipitate with excess AgNO3
solution, two chloride ions must be released, ie, two chlorine atoms should be
outside. As the coordination of 𝐶𝑜 ion is 6, in addition to one chlorine atom five NH3
molecules will be present in coordination sphere.
Formula is [Co( NH 3 )5 Cl ]Cl2
and number of ions obtained per molecule is 3.
[Co( NH 3 )5 Cl ]2   2Cl 
[Co( NH 3 )5 Cl ]Cl2 

1
Difference between complex compound and a double salt :

A double salt dissociates completely into ions when it is dissolved in water.

 K   Al 3  SO42
Eg. K 2 SO4 . Al2 ( SO4 )3 .24 H 2O 
i.e, all the ions of a double salt can be identified.
While a complex compound dissociates partially, ie, all the ions cannot be
identified.
 4 K   [ Fe(CN )6 ]4 
Eg. K 4 [ Fe(CN )6 
i.e, K  can be identified but Fe2 or CN  cannot be identified.
Important definitions :
(a) Coordination entity :
A coordination entity constitutes a central metal atom or ion bonded to a fixed
number of ions or molecules.
Eg. (i) [ Ni (CO ) 4 ]
(ii) In [Co( NH 3 ) 6 ]Cl3 , [Co( NH 3 ) 6 ]3 is the coordination entity.
(b) Central metal atom or ion :
The atom or ion present in a coordination entity to which a fixed number of ligands
are bound in a definite geometrical arrangement around it is called central metal atom (or)
ion.
Eg. (i) In K 4 [ Fe(CN )6 ], Fe 2  is central metal ion
(ii) In [ Ni (CO ) 4 ], Ni is the central metal atom
(c) Ligand :
The ion or molecule bound to the central atom/ion in a given coordination
compound is called ligand.
 Ligand may be neutral molecule like NH3 , anion like Cl  or cation like NO  .
 When a ligand is bound to the central metal atom through a single donor atom then it
is called monodentate (or) unidentate ligand.
Eg. Cl  , H 2O, NH 3 etc.
 When a lignad is bound to a metal ion through two donor atoms then it is called
didentate (or) bidentate ligand.
Eg. Ethane-1,2-diamine (en); oxalate etc.

The ligand which can ligate through two different atoms is called ambidentate
ligand.
 
Eg. NO2 , SCN , etc
 The ligand which contains several donor atoms is called polydentate ligand.
Eg. EDTA  hexadentate
 When a didentate (or) polydentate ligand uses its two or more donor atoms to bind a
single metal ion then it is said to be a chelate ligand.
 The number of ligating groups present in a given ligand is called denticity.
(d) Coordination number:
The number of ligand donor atoms to which the central metal/ion is directly bonded is
called coordination number.
Eg. [ PtCl6 ]2 
 Coordination number is 6.
[ Ni(CO)4 ] 
 Coordination number is 4.
[ Fe(C2O4 )3 ]3 
 Coordination number is 6 etc.
(e) Coordination sphere:
The part of the complex compound in which the central metal/ion and the ligands
attached to it are enclosed in square bracket is collectively called coordination sphere.
 Ionisable spheres are written outside the bracket and are called counter ions.
Eg. In K 4 [ Fe(CN ) 6 ],[ Fe(CN ) 6 ]4 is coordination sphere and K  ions are counter ions.
 The special arrangement of the ligand atoms which are directly attached to the
central atom/ion defines a coordination polyhedron about the central atom.
Eg. Octahedral, square planar, tetrahedral etc.

2
(f) Oxidation number:
The charge carried by central metal atom when all the ligands are removed along with
the electron pairs that are shared with the central atom is called oxidation number.
3
Eg. In [Cu (CN )4 ] , the oxidation state of copper is +1 and represented as Cu(I).
(g) Homoleptic complexes :
Complexes in which a metal is bound to only one kind of donor groups are called
homoleptic complexes.
Eg. [Co( NH 3 ) 6 ]3 ,[ Fe(CN ) 6 ]4 etc.
(h) Heteroleptic complexes:
Complexes in which a metal is bound to more than one kind of donor groups is called
heteroleptic complexes.
Eg. [Co( NH 3 ) 4 Cl2 ] ,[ Pt ( NH 3 ) 2 Cl ( NO2 )] etc.
Nomenclature of the coordination compounds :
Rules to be followed :
(1) The cation is to be named first in both positively or negatively charged coordination
entities.
(2) The ligands are named in an alphabetical order before the name of the central
atom/ion.
(3) Names of the anionic ligands end in ‘O’. Neutral and cationic ligands are the same.
Special names : H 2O  aqua
NH 3  amine
CO  Carbonyl
NO  Nitrosyl
(4) Prefixes like di, tri, tetra etc are used to indicate the number of the individual
ligands in the coordination entity.
If the names of the ligands include a numerical prefix, then the terms bis,
tris, tetrakis are used.
(5) The oxidation number of the metal in cation, anion or neutral coordination entity is
indicated by Roman numerical in parenthesis.
(6) If the complex ion is a cation, the metal is named as the element.
If the complex ion is an anion, the name of the metal ends with the suffix ate.
If the complex molecule is neutral the metal is named as the element.
Examples :
(a) [Cr ( NH 3 )3 ( H 2O)3 ]Cl3  Triamminetriaqua chromium (III) chloride
(b) [Co( H 2 NCH 2CH 2 NH 2 )3 ]2 (SO4 )3  Tris(ethan-1,2-diamine) cobalt(III) sulphate
(c) [ Ag ( NH 3 )2 ][ Ag (CN )2 ]  Diammine silver (I) dicyano argentate (I)
(d) [ Pt ( NH 3 )2 Cl ( NO2 )]  Diammine chlorido nitrito-N-Platinum (II)
(e) K3[Cr (C2O4 )3 ]  Potassium trioxalato chromate (III)
(f) [CoCl2 (en ) 2 ]Cl  Dichlorido bis (ethan-1,2-diammine) cobalt(III) chloride
(g) [Co( NH 3 )5 (CO3 )]Cl  Pentammine carbonato cobalt (III) chloride
(h) Hg [Co ( SCN ) 2 ]  Mercury tetrathiocyanoto cobaltate (III)
(i) [Co( NH 3 )6 ]Cl3  Hexamnine cobalt (III) chloride
(j) [Co( NH 3 )5 Cl ]Cl2  Pentaammine chlorido cobalt (III) chloride
(k) K3[ Fe(CN )6 ]  Potassium hexacyano ferrate (III)
(l) K3[ Fe(C2O4 )3 ]  Potassium trioxalato ferrate (III)
(m) K 2 [ PdCl4 ]  Potassium tetrachlorido pelladate (II)
(n) [ Pt ( NH 3 )2 ( NH 2CH 3 )]Cl  Diamnine chlorido methanamine platinum (II) chloride
Isomerism in coordination compounds :
 The compounds containing same molecular formula but differ in their physical or
chemical properties are called isomers.
In complex compounds isomerism is mainly due to different arrangement of atoms.

3
Structural Isomerism :
(a) Linkage isomerism :
(i) Linkage isomerism is possible in the complex compounds containing ambidentate
ligand.
(ii) The ambidentate ligand contains two different donor atoms but at a time only
one atom is directly linked to the central metal atom of the complex due to which two
different complexes are possible with same molecular formula. These are called linkage
isomers.
Eg. (1) [Co( NH 3 )5 NO2 ]Cl2 &[Co( NH 3 )5 ONO]Cl2
(2) [ Pd (dipy)( SCN ) 2 ] & [ Pd (dipy)( NCS ) 2 ]
(b) Ionisation isomerism :
The compounds containing same molecular formula but give different ions in
solution are called ionisation isomers.
Eg. (1) [Co( NH 3 )5 Br ]SO4 &[Co( NH3 )5 So4 ]Br
2
I Compound gives So4 ion in solution while II compound gives Br  ion in solution.
(2) [Co( NH3 )4 Cl2 ]NO2 &[Co( NH3 )4 Cl ( NO2 )]Cl
(c) Hydrate isomerism :
The compounds with same molecular formula but differ in the number of water
molecules present inside and outside the coordination sphere are called hydrate isomers
(or) solvate isomers.
Eg. (1) [Cr ( H 2O)6 ]Cl3 &[Cr ( H 2O)5 Cl ]Cl2 .H 2O
(2) [Co( NH 3 )4 ClH 2O]Br &[Co( NH3 )4 Br2 ]Cl.H 2O
(d) Coordination isomerism :
The compounds containing same molecular formula but having different nature of
lignads in cationic and anionic complexes are called coordination isomers.
This type of isomerism is possible in the coordination compounds having both
cationic and anionic complexes.
Eg. (1) [ Pt ( NH 3 )4 ][CuCl4 ]&[Cu( NH3 )4 ][ PtCl4 ]
(2) [Cr ( NH 3 )6 [Co(C2O4 )3 ]&[Co( NH 3 )6 [Cr (C2O4 )3 ]
Stereo Isomerism :
(a) Geometrical isomerism :
The compounds with same molecular formula but having different possible
geometric arrangements of ligands are called geometrical isomers.
(i) MX 2 L2 has two geometrical square planar isomers.
L X L X

M & M

L X X L
Cis Trans
(ii) MABXL  square planar complex has three geometrical isomers, two cis and one
trans. A L A B
A B
M M
M
X B X L
L X
MX 2 L4  Octahedral.
X X
L X L L

M M

L L L L
L X
(Cis) (Trans)

4
[CoCl2 (en ) 2 ]  Octahedral

Cl Cl
Cl
en M en Co en

en Cl

MA3 L3  Octahedral (Cis) (Trans)

(i) Three donor atoms occupy adjacent positions at the corners of the octahedral face, then
it is called facial (fac) isomer.
NH3
O 2N NH3

Co

O 2N NH3
NO2 (fac)

(ii) When the positions are around the meridian of the octahedron, then it is called
meridional isomer.
NH3
O 2N NH3

Co

O 2N NO2
NH3 (mer)

Optical isomerism :
(i) The compounds with same molecular formula but differ in their behaviour towards
plane polarised light are called optical isomers.
The two forms are called dextro (d) with rotates the plane polarised light towards right
and laevo(l) which rotates the plane polarised light towards left.
Eg. (1) [Co(en)3 ]3

en en

en Co Co en

en en

(d) (l)
(2) [ Pt (en ) 2 Cl2 ]
Cl Cl
Cl
Cl
en Pt en
Pt

en
en
(d) (l)

Valence Bond Theory :

 According to this theory the central metal atom (or) ion undergoes hybridisation using
its (n – 1)d, ns, np (or) ns, np, nd orbitals.

5
  Based on the hybridisation, the complex gets definite geometrical shape.
S.No. Coordination Nature of Shape
Number hybridisation
1 4 𝑑𝑠𝑝 Square planar

2 4 𝑠𝑝 Tetrahedral

3 5 𝑠𝑝 𝑑 Trigonal bipyramidal

4 6 𝑑 𝑠𝑝 Octahedral

5 6 𝑠𝑝 𝑑 Octahedral

 Coordination number – 4 :
2
(a) [ NiCl4 ]  Ni 2 undergoes sp3 hybridisation.

Ni 2  3d 8 4s 0 4 p0

Hence one 4s orbital and three 4p orbitals undergo hybridisation. The resulting
3
four sp hybrid orbitlas accept lone pairs from four Cl  ions to give a tetrahedral complex.

[ NiCl4 ]2 

3d 𝑠𝑝
It is a high spin complex, paramagnetic due to the presence of 2 unpaired electrons
and it is also known as outerorbital complex.

2 2
(b) [ Ni (CN )4 ] :- Here Ni 2 undergoes dsp hybridisation.
3𝑑 4𝑠 4𝑝
Ni 2 :-

Ni 2 (after dsp2 ) :
3𝑑 (𝑑𝑠𝑝 ) 4p

[ Ni(CN )4 ]2 :-
3𝑑 (𝑑𝑠𝑝 ) 4p

Ni 2 uses one 3d orbital, one 4s orbital and two 4p orbitals for hybridisation. The
2
resulting four dsp hybrid orbitals accepts lone pairs from four CN  ions giving square
planar complex.
It is a low spin complex, diamagnetic due to the absence of unpaired electrons and
known as innerorbital complex.
3
(c) [ Ni (CO ) 4 ] : In this complex Ni atom is in zero oxidation state and undergoes sp
hybridisation by using one 4s and three 4p orbitals.
3𝑑 4𝑠 4𝑝
Ni :
10 0 0
Ni (after rearrangement of electrons) : 3d 4s 4 p

𝑠𝑝
[ Ni (CO ) 4 ] : 3d 10 (4s  4 p)

𝑠𝑝

As the complex does not contain unpaired electrons, it is diamagnetic

and tetrahedral due to 𝑠𝑝 hybridisation.

6
 Coordination Number - 6 :
2 3
(a) [Co ( NH 3 ) 6 ]
3
: Here Co3 ion undergoes d sp hybridisation.
3𝑑 4𝑠 4𝑝
3
Co :

Co3 (after rearrangement of electrons)

𝑑 𝑠𝑝 hybrid orbitals

[Co( NH 3 ) 6 ]3 :
3𝑑 𝑑 𝑠𝑝

Co3 uses two 3d, one 4s and three 4p orbitals for hybridisation. It is an
innerorbital complex or low spin complex. As the complex does not contain unpaired
electrons, it is diamagnetic.
3 2
(b) [CoF6 ]3 : Here Co3 ion undergoes sp d hybridisation.

3𝑑 4𝑠 4𝑝 4𝑑
Co3 :

3𝑑 𝑠𝑝 𝑑 4p
3 3 2
Co ( sp d ) :

3d 𝑠𝑝 𝑑 4p
3
[CoF6 ] :

Here Co3 uses one 4s, three 4p and two 4d orbitals for hybridisation. It is
an outerorbital complex and high spin complex. As it contains unpaired electrons, it is
paramagnetic. Shape is octahedral.
2 3
(b) [Co( NH 3 ) 6 ]3 : Here Co3 undergoes d sp hybridisation.

3𝑑 4s 4p 4d
3
Co :

Co3 [After rearrangement] :

3d 𝑑 𝑠𝑝 4d

3d 𝑑 𝑠𝑝 4d
3
[Co( NH 3 ) 6 ] :

Here Co3 uses two 3d, one 4s and three 4p orbtials for hybridisation. It is an
innerorbital complex or low spin complex. As the complex does not contain unpaired
electrons, it is diamagnetic. Shape is octahedral.
 [ Mn(CN ) 6 ]3 has less paramagnetic behaviour while [ MnCl6 ]3 has high
paramagnetic behaviour.
Reason : In [ Mn(CN ) 6 ]3 , Mn3 undergoes 𝑑 𝑠𝑝 hybridisation.
3𝑑 4𝑠 4𝑝
3
Mn :

3d

[ Mn(CN ) 6 ]3 :
𝑑 𝑠𝑝
Number of unpaired electrons is 2.
While in [ MnCl6 ]3 , Mn3 undergoes 𝑠𝑝 𝑑 hybridisation.

7
 3𝑑 4𝑠 4𝑝 4𝑑
Mn3 :

3d 𝑑 𝑠𝑝 4p
3
[ MnCl6 ] :

Number of unpaired electrons is 4.

As [ MnCl6 ]3 contains more number of unpaired electrons, it is more paramagnetic than
[ Mn(CN ) 6 ]3 .
 The magnetic moment of [ FeF6 ]3 is higher than that of [ Fe(CN ) 6 ]3 .
3 2
Reason : In [ FeF6 ]3 , Fe3 ion undergoes sp d hybridisation giving five unpaired electrons
2 3
while in [ Fe(CN ) 6 ]3 , Fe3 in undergoes d sp hybridisation giving one unpaired electron.

 [CoF6 ]3 is paramagnetic while [Co (C 2O4 )3 ]3 is diamagnetic, give reason.
3 2
Reason : In [CoF6 ]3 , the Co3 ion undergoes sp d hybridisation giving four unpaired
2 3
electrons while in [Co (C 2 O4 )3 ]3 the Co3 ion undergoes d sp hybridisation giving zero
unpaired electrons.

Limitations of VBT :

1) It does not give quantitative interpretation of magnetic data.

2) It does not explain the colour exhibited by coordination compounds.

3) It does not give quantitative interpretation of the thermodynamic or kinetic stability of

coordination compounds.

4) It does not distinguish between weak and strong ligands.

Crystal Field Theory :

(1) According to CFT, the bonding in complex ions is purely electrostatic. This theory
considers the ionic ligands like 𝐹 , 𝐶𝑙 etc as negative point charges and the neutral
ligands as dipoles where the negative end pointing towards central metal ion.
(2) Around the central metal ion ligands are surrounded in such a way that the repulsion
between these negative point charges in minimum.
(3) The five d-orbitals are divided into two sets; dxy, dyz, dzx as one set called t2g orbitals
and d x2  y 2 and d z 2 as another set called eg set.
(4) When the ligands approach the central metal ion then electrons of d-orbitals of the
metal get repelled by the lone pairs of the ligands. As a result, the d-orbitals of
central metal split into two sets of orbitals having different energies. This is called
crystal field splitting.
(5) The extent of splitting depends upon the number of ligands and their position around
the metal atom or ion.
Splitting of d-orbitals in octahedral complexes :

In a octahedral complex, metal ion is placed at the centre of the octahedron and the
surrounding six ligands occupy the six corners of the octahedron.

When the ligands are approaching, since the two lobes of two eg- orbitals lie in the
path of approaching ligands, the electrons of these orbitlas experience greater repulsion
than those in t2g orbitals whose lobes are directed in space between the path of the
ligands, ie, energy of eg- orbitals is increased while that of t2g orbitals is decreased.

The energy difference between these two sets of orbitals is called crystal field
splitting energy. It is represented by 0.
eg

0 10 dq.

t2g
8
 Energy of t2g orbitals is 0.4 0 less than that of average energy while the energy of
eg orbitals is 0.6 0 greater than that of average energy.

Distribution of d-electrons in t2g and eg- orbitals in octahedral complexes :

Based on the nature of the ligands, the distribution of d-electrons in t2g and eg-
orbitals takes place.

(a) When the ligands are weak field ligands :

Under the influence of weak field ligands, the energy difference between t2g and eg
sets is relatively small, ie, all the d-orbitals have nearly the same energy and the
distribution of electrons in t2g and eg orbitals takes place according to the Hund’s rule.

t2 g1,2,3 
 eg 4,5 
 t2 g 6,7,8 
 eg 9,10

(b) When the ligands are strong field ligands :

Under the influence of strong field lignads the energy difference between t2g and
eg. Sets is relatively high, hence the distribution of electrons does not obey Hund’s rule.
The first six electrons will go to t2g orbitals and the next four electrons will go to eg.
orbitals

t1,2,3,4,5,6
2g 
 eg 7,8,9,10

Strong field (High spin) complexes Weak field (low spin complexes)

𝑑 Configuration No.of unpaired Spin Configuration No.of unpaired Spin

electrons electrons

d1 t2 g1 eg 0 1 1/2 t2 g1 eg 0 1 1/2

d2 t2 g 2 eg 0 2 1 t2 g 2 eg 0 2 1

d3 t2 g 3 eg 0 3 3/2 t2 g 3 eg 0 3 3/2

d4 t2 g 4 eg 0 2 1 t2 g 3 eg 1 4 2

d5 t2 g 5 eg 0 1 1/2 t2 g 3 eg 2 5 5/2

d6 t2 g 6 eg 0 0 0 t2 g 4 eg 2 4 2

d7 t2 g 6 eg1 1 1/2 t2 g 5 eg 2 3 3/2

d8 t2 g 6 eg 2 2 1 t2 g 6 eg 2 2 1

d9 t2 g 6 eg 3 1 1/2 t2 g 6 eg 3 1 1/2

d 10 t2 g 6 eg 4 0 0 t2 g 6 eg 4 0 0

P  Average pairing energy which is the energy required to pair two electrons in the same
orbital.

0  Octahedral crystal field splitting energy.

Crystal field splitting in tetrahedral complexes :

In the tetrahedral arrangement of four ligands surrounding the metal ion, the three
t2g orbitals are close to the approaching ligands. As a result, the t2g electrons experience
more repulsion than eg- electrons, ie, the energy of t2g orbitals increases while that of eg-
decreases.
t2g

t 10 dq.

9
eg
 The energy gap between two sets of orbitals is designated as t, where t < 0.

4
t  0
9

Distribution of d-electrons in t2g and eg orbitals in tetrahedral complexes :

Based on the nature of the ligands, the d-electrons are distributed in t2g and eg-
orbitals as follows.

Weak field (High spin) complexes Strong field (low spin complexes)
𝑑 Configuration No.of unpaired Spin Configuration No.of unpaired Spin
electrons electrons

d1 t2 g 0 eg1 1 1/2 t2 g 0 eg1 1 1/2

d2 t2 g 0 eg 2 2 1 t2 g 0 eg 2 2 1

d3 t2 g1 eg 2 3 3/2 t2 g 0 eg 3 1 1/2

d4 t2 g 2 eg 2 4 2 t2 g 0 eg 4 0 0

d5 t2 g 3 eg 2 5 5/2 t2 g1 eg 4 1 1/2

d6 t2 g 3 eg 3 4 2 t2 g 2 eg 4 2 1

d7 t2 g 3 eg 4 3 3/2 t2 g 3 eg 4 3 3/2

d8 t2 g 4 eg 4 2 1 t2 g 4 eg 4 2 1

d9 t2 g 5 eg 4 1 1/2 t2 g 5 eg 4 1 1/2

d 10 t2 g 6 eg 4 0 0 t2 g 6 eg 4 0 0

Magnetic nature :
The complexes in which metal ion/atom has unpaired electrons is paramagnetic
and it possesses a definite magnetic moment.
Magnetic moment (𝜇) = 𝑛(𝑛 + 2) 𝐵𝑀
Where n = number of unpaired electrons
eh
BM   9.274  10 21 erg. gauss -1
4 mc
Eg : [ Fe( H 2O ) 6 ] with four unpaired electrons is paramagnetic while [ Fe (CN ) 6 ]4 
2

with zero unpaired electrons is diamagnetic.

Magnetic moment of [ Fe( H 2O ) 6 ]2  is
  n( n  2) BM
 4( n  2) BM
= 4.9 BM.
Colour :
 When the energy of the incident photon is equal to the difference between the lower
and higher d-orbital energy levels, then an electron is promoted from a lower to
higher level. If the wavelength of the photon absorbed by an ion lies inside the
visible region, then the complex ion shows colour.
 Based on the colour of the light observed the complex appears with a particular
complimentary colour.
 For a given metal ion, some ligands cause a small energy separation of d-orbitals
while others cause a large separation. Hence different ligands may bring different
colours to the complex ions of the same metal ion.
Complex ion Colour of light Colour of the
absorbed complex observed
[CoF6 ]3 Red Green
[Co( H 2O ) 6 ]3 Yellow Blue-Green
[Co( NH 3 ) 6 ]3 Blue Yellow-Orange
[Co(CN )6 ]3 UV Pale-Yellow

10
  𝐹 ions cause the smallest splitting while 𝐶𝑁 ions cause the largest splitting.
Spectrochemical series :
When the ligands are arranged in the order of the magnitude of crystal field
splitting, then that order of ligands is called spectrochemical series.

I   Br   Cl   NO3  F   OH   Ox 2   H 2O  Py
(weak field ligands)
NH 3  en  dipy  o  phen  NO2  CN   CO
(strong field ligands)

Bonding in metal carbonyls :

In metal carbonyls, the central metal has zero oxidation state.
The metal-carbon bond in metal carbonyls possess  and  bonds. The M-C ‘’
bond is formed by the donation of lone pair of electrons on the carbonyl carbon to a
vacant orbital of metal while the M-C -bond is formed by the donation of a pair of
electrons from a filled d-orbital of metal to the vacant antibonding  * orbital of
carbonmonoxide. The metal ligand bond creates a synergic effect which strengthens the
M-C bond.
Structures of metal carbonyls :
(i) Ni (CO ) 4  Tetrahedral (ii) [ Fe(CO)5 ]  Trigonal bipyramidal (iii) [Cr(CO)6 ]  Octahedral
CO CO CO
OC CO
OC
Ni Fe CO Cr
CO CO OC
CO CO OC CO
CO
(iv) [ Mn2 (CO)10 ] (v) [Co2 (CO)8 ]

CO CO OC CO CO
CO CO
OC Mn CO OC CO CO CO
Mn

OC OC OC CO CO
CO CO
Stability of coordination compounds :
The magnitude of the equilibrium constant for the association quantitatively
expresses the stability.
Larger the stability constant value, larger is the stability of the complex.
Eg. For ML4 .

M  4L ML4
[ML4 ]

[ M ][ L]4
[ ML]
M L ML; K1 
[ M ][ L]
[ ML2 ]
ML  L ML2 ; K 2 
[ ML][ L]

[ ML3 ]
ML2  L ML3 ; K 3 
[ ML2 ][ L]
[ ML4 ]
ML3  L ML4 ; K 4 
[ ML3 ][ L]
Where,   K1.K 2 .K3 .K4 .
 is called overall stability constant and k1 , k2 , k3 , k4 are called stepwise stability
constants.
The reciprocal of the stability constant is called instability constant or dissociation
constant.

*******
11