COORDINATION COMPOUNDS

Addition compounds : They are formed by the combination of two or more stable
compounds in stiochiometric ratio. [CBSE 2019] [1M]

• Compounds which lose their identity in • Compounds which does not lose their
solution are called double salts identity in solution are called coordination
compounds

• K2SO4 +Al2(SO4)3 + 24H2O • Fe(CN)2 + 4KCN → K4[Fe(CN)6]

Aq. + +
4K (aq)


[Fe(CN)6 ]4 − (aq)
K2SO4·Al2(SO4)3·24H2O [Alum]

H2O (aq)

2K+(aq) + 2Al+3(aq) + 4 SO 24 − (aq)

Terminology related to co-ordination compound

(a) Co-ordination entity: The central atom/ion and the ligands attached to it are enclosed
in square brackets are collectively known as co-ordination entity or co-ordination
sphere.
Ligand: The donor atoms ions or molecules which donate a pair of electrons to the
central metal atom/ion are called ligands.
For example: [Fe(CN)6]4–, [Co(NH3)6]3+
4– NH 3+
CN .. 3
NC CN H3N: :NH3
Fe Co
NC CN H3N: :NH3
..
CN NH3

(b) Denticity: The no. of donor atoms present in a ligand, is called denticity of ligand.

• Unidentate: Only one donor atom [Cl– / NH3 / H2O etc.]

• Bidentate / didentate: When a ligand can bind through two donor atoms.

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 1 2
For example: Ethane-1, 2-diamine [NH 2 — C H 2 — C H 2 —NH 2 ] or Ethylenediamine
[en]
..
NH2
CH2
M+
.. CH2
NH2

• Polydentate: More than two donor atoms.

For example: Ethylene diamine tetra-acetate ion
O
||
. . CH2—C—O
N
CH2—C—O
||
O M+
O
||
. . CH2—C—O
N
CH2—C—O
||
O
• [EDTA]4– : Hexadentate Ligand

• It can bind through two nitrogen and four oxygen atoms to a central metal ion.
(c) Ambidentate ligand: Unidentate ligands containing more than one co-ordination
atoms are ambidentate ligand.
For example:

(d) Co-ordination Number: The no. of ligand donor atoms to which the metal is directly
bonded.
For example: [PtCl6]2– : C.N.  6

[Ni(NH3)4]2+ : C.N.  4

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(e) Co-ordination Polyhedron: The spatial arrangement of the ligand atoms which are
directly attached to the central atom/ion defines a co-ordination polyhedron about the
central atom.

(f) Homoleptic and heteroleptic complexes:

• Complexes in which a metal is bound to only one kind of donor groups are known
as homoleptic.
For example: [Co(NH3)6]3+

• Complexes in which a metal is bound to more than one kind of donor groups are
known as heteroleptic complex
For example: [Co(NH3)4Cl2]+

Formula IUPAC Name Formula IUPAC Name

Pyridine NO Nitrosyl

NH 3 Ammine NO 2− Nitrito-N / Nitro

H2O Aqua ONO– Nitrito-O

CO Carbonyl NH 2− Amido

R—NH2 Alkyl amine

Oxalato [ Ox2– ]
Cl– Chlorido

Br– Bromido OH– Hydroxo

CN– Cyanido/cyano

CO 3− Carbonato

SCN– Thiocyanato

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(g) Oxidation No. of central atom:
Oxidation no. of CA + sum of charge on total ligands = charge on co-ordination sphere.
[Cu(NH3)4]2+ : Oxidation no. of Cu ??
x + 4 (charge on NH3) = 2
x + 4 * 0 = 2 then x = +2

Nomenclature of Co-ordination Compounds

Rules for writing formula of mononuclear co-ordination complexes
(a) Formula of cation [simple or complex] is written first.
(b) Co-ordination entity is enclosed in square bracket.
(c) In coordination sphere, metal atom is written first, followed by ligands in alphabetical
order of their names.
(d) In abbreviated ligands [like en/Ox] → first letter of abbreviation is considered
(e) When ligands are polyatomic, their formulas are enclosed in parenthesis.
For example: (SCN), (PPh3) etc.
(f) There should be no space between the ligands and the metal.
(g) For charged coordination entity: Charge is indicated outside the square brackets as a
right superscript with the no. before the sign.
For example: [Co(CN)6]3–, [Cr(H2O)6]3+ etc.
(h) The charge of the cation is balanced by the charge of anion.
For example: [Cr(H2O)5Cl] Cl2·H2O

Alphabetical order: Aqua > Chloro

Rules for naming of mononuclear co-ordination compounds

(a) Complex cation is named first followed by anion (if present).
(b) The ligands are named in alphabetical order before the name of metal atom/ion.
(c) Names of anionic ligands end in ‘O’. [For example: Cyano/chlorido]
Neutral ligands have no special ending [H2O → Aqua, NH3 → ammine]
Positive ligands end in ‘ium’. [NO+: Nitrosonium]
(d) Prefixes mono, di, tri …. are used to indicate the number of the individual ligands.

• When the names of ligands include a numerical prefix, then terms bis,tris,tetrakis
are used, the ligand to which they refer being placed in paranthesis.
(e) Oxidation state of metal is indicated by roman numerical in parenthesis.
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(f) If complex ion is a cation, the metal is named same as the element.

• If complex ion is an anion, the name of the metal ends with suffix ‘ate’.

• The neutral complex molecule is named similar to that of the complex cation.

1. [Cr(NH3)3(H2O)3]Cl3 : triamminetriaquachromium(III)chloride
Oxidation no. of Cr + 3(charge on NH3) + 3(charge on H2O) + 3(charge on chlorine) = 0

• Oxidation no. of Cr + 3*0 + 3*0 + 3*(–1) = 0

• Oxidation no. of Cr = +3
2. [Co(NH2—CH2—CH2—NH2)3]2 (SO4)3 : Tris(ethane-1,2-diamine)cobalt(III)sulphate

• 2(x + 3*O) + 3(–2) = 0

• x = +3

3. [Ag(NH3)2] [Ag(CN)2] : Diamminesilver(I)dicyanoargentate(I)

+ve complex ion –ve complex ion

4. Ni(CO)4 : Tetracarbonylnickel(0)

x + 4(0) = 0 then x = 0

5. K4[Fe(CN)6] : Potassiumhexacyanidoferrate (II).

4(+1) + x + 6(–1) = 0 then x = + 2

6. [Pt(en)2Cl2]2+ : Dichloridobis(ethane-1,2-diamine)platinum(IV)ion. [CBSE 2015] [1M]

7. [Ni(NH3)6]Cl2 : Hexaammine nickel (II) chloride. [CBSE 2015(C)] [1M]
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8. [PtCl(NH2CH3)(NH3)2]Cl : Diammine chlorido methylamine platinum (II) chloride.
[CBSE 2011(C)]
9. [Pt(NH3)4Cl2]Cl2 : Tetraamminedichlorido platinum (IV) chloride. [CBSE 2011(C)]
10. [Cr(NH3)6] [Co(CN)6] : Hexaammine chromium(III) hexacyanocobaltate (III)
+ve complex –ve complex [CBSE 2011(C)]
11. [Pt(NH3)3(NO)Cl2]Br2 : Triammine dichlorido nitrosyl platinum (IV) bromide.[CBSE 2011(C)]
12. [Co(CN)2(NH3)4]Cl : tetraammine dicyano cobalt (III) chloride. [CBSE 2011(C)]

13. [Cr(NH3)5(NCS)] [ZnCl4] : Pentaammineisothiocyanatochromium(III) etrachloridezincate (II)

+ve complex –ve complex [CBSE 2011(C)]
14. [Co(NH3)5Cl]Cl2 : Pentaammine chlorido cobalt (III) chloride. [CBSE 2010(C)]
15. [Cr(NH3)2Cl2(en)]Cl : Diammine dichlorido(ethane-1,2-diamine) chromium (III) chloride.
[CBSE 2015]
16. K3[Fe(CN)6] : Potassiumhexacyanoferrate(III) [CBSE 2015]
17. [Co(NH3)6]Cl3 : Hexammine cobalt (III) chloride. [CBSE 2015]
18. [Co(en)3]3+ : Tris(ethane-1, 2-diamine) cobalt (III) ion. [CBSE 2018(C)]
19. [NiCl4]2– : Tetrachloridonickelate (II) ion. [CBSE 2015 / CBSE 2014(C)][1M]
20. [Co(NH3)5(NO2)]2+ : Pentaamminenitrito-N cobalt (III) ion.
21. [Pt(NH3)2Cl2] : Diammine dichloridoplatinum (II)

• Co-ordination no. = 4

• Oxidation state = +2
3−
  COO−  
22. Co  |   : trioxalato cobaltate (III) ion. [CBSE 2014] [3M]
  COO−  
 3

23. [Cr(CO)6] : Hexacarbonylchromium (0) [CBSE 2014] [3M]

24. [PtCl3(C2H4)] : Trichloridoethene platinum (IV) [CBSE 2014] [3M]
25. [CoBr2(en)2]+ : Dibromidobis (ethane-1, 2-diamine) cobalt (III) ion. [CBSE 2013]
26. K3[Fe(C2O4)3] : Potassiumtrioxalatoferrate (III) ion. [CBSE 2013(C)]
27. [Pt(NH3)6]Cl4 : Hexaamine platinum (IV) chloride. [CBSE 2013(C)]
28. [Cr(C2O4)3]3– : Trioxalatochromate (III) ion.
29. [Co(en)2Cl2]+ : Dichloridobis (ethane-1, 2-diamine) cobalt (III) ion.
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30. Hexaammine cobalt (III) sulphate : [Co(NH3)6]2(SO4)3 [CBSE 2019] [2M]
31. Potassiumtrioxalatochromate (III) : K3[Cr(C2O4)3] [CBSE 2019] [2M]
32. Potassium trioxalato aluminate (III) : K3 [Al(C2O4)3] [CBSE 2017] [2M]
33. Dichloridobis (ethane-1, 2-diamine) cobalt (III) ion : [CoCl2(en)2]+ [CBSE 2017] [2M]
34. Pentaamminenitrito-O-cobalt (III) ion : [Co(NH3)5(ONO)]2+ [CBSE 2015] [1M]
35. Sodiumdicyanidoaurate(I) : Na[Au(CN)2] [CBSE 2017] [2M]
36. Tetraammine chloridonitrito-N-platinum (IV) sulphate : [Pt(NH3)4Cl(NO2)]SO4
[CBSE 2017] [2M]
37. Mercury tetrathiocyanatocobaltate (III) : Hg[Co(SCN)4]
38. Potassium trioxalato aluminate (III) : K3[Al(C2O4)3]
39. Potassium tetrahydroxozincate (II) : K2[Zn(OH)4]

Werner’s Theory: Werner was the first to formulate his idea about the structures of
coordination compounds.

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 Experiments: (1) In a series of compounds of cobalt (III) chloride with ammonia, it was
found that some of chloride ions could be precipitated as AgCl on adding excess
AgNO3 solution but some remained in solution.
AgNO
• CoCl3  6NH3 ⎯⎯⎯⎯ 3
Excess
→ 3 mol AgCl

→ 3 AgCl + [Co(NH 3 )6 ]3+

AgNO
[Co(NH3 )6 ]Cl3 ⎯⎯⎯⎯ 3
Excess

Secondary valency is satisfied by → 6NH3 [Coordination no. = 6]

Primary valency is satisfied by → 3Cl– [Co in (III) oxidation state]
AgNO
• CoCl3  5NH3 ⎯⎯⎯⎯ 3
Excess
→ 2 mol AgCl

→ 2 AgCl + [Co(NH 3 )5 Cl]2+

AgNO
[Co(NH 3 )5 Cl]Cl2 ⎯⎯⎯⎯ 3
Excess

Secondary valency in satisfied by → 5NH3 and 1Cl– [Coordination no. = 6]

Primary valency in satisfied by → 3Cl– [Co in (III) oxidation state]

AgNO
• CoCl3  4NH 3 ⎯⎯⎯⎯ 3
Excess
→ 1 mol AgCl

→ [Co(NH 3 )4 Cl 2 ]+ + AgCl
AgNO
[Co(NH 3 )4 Cl2 ]Cl ⎯⎯⎯⎯ 3
Excess

Secondary valency is satisfied by → 4NH3 and 2Cl– [Coordination no. = 6]

Primary valency is satisfied by → 3Cl– [Co in (III) oxidation state]
(2) As we know conductivity of a solution depends on no. of ions present in solution.
Experimental order of conductivity: CoCl3·6NH3 > CoCl3·5NH3 > CoCl3·4NH3

No. of ions in their solution [per mole of electrolyte] : 4 3 2

1[Co(NH3)6]3+ 1[Co(NH3)5Cl]2+ 1[Co(NH3)4Cl4]+

3Cl– 2Cl– 1Cl–

• When a coordination compound CrCl3·6H2O is mixed with AgNO3, 2 moles of AgCl

are precipitated per mole of compound.
(i) Write structural formula:

→ 2AgCl  : means that 2Cl − is ionisable

AgNO
CrCl3  6H 2O ⎯⎯⎯⎯
3


[Cr(H 2O)5 Cl]Cl 2  H 2O

[Delhi 2014/2016 CBSE 29109] [1M]

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(ii) IUPAC name of complex : Pentaaquachloridochromium(III)chloride. [Delhi 2014] [1M]

VALENCE BOND THEORY

• According to this theory, the metal ion or atom under the influence of ligand can use
its
(n – 1)d, ns, np / ns, np, nd orbitals for hybridization to give a set of equivalent
orbitals of definite geometry.

• These hybridized orbitals are allowed to overlap with ligand orbitals that can denote
electron pairs for bonding.

• It is possible to predict the geometry of a complex from the knowledge of its

magnetic behaviour on the basis of VBT.

• Magnetic moment of a complex on no. of unpaired electrons.

Magnetic moment  = n(n + 2)

n = no. of unpaired electron.

Example: (i) [Co(NH3)6]3+ : Diamagnetic in nature. [CBSE 2010] [2M]

• Co+3 ion :
(3d6) 3d 4s 4p

• Hybridisation :
[d2sp3]
Inner orbital d2sp3 : Inner orbital complex

Diamagnetic
Electrons are period

NH3 NH3 NH3 NH3 NH3 NH3

6 ligands : octahedral
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(ii) [CoF6]3– : Paramagnetic octahedral complex [CBSE 2018, 2014(C), 2010]
Presence of unpaired electrons.

Co+3 ion :
(3d6) 3d 4s 4p 4d

Hybridisations :

sp3d2 hybrid

[CoF6]3– :
[Outer orbital
complex] F– F– F– F– F– F–

(iii) [NiCl4]2– : Paramagnetic in nature. [CBSE 2017]

Ni2+ ion :
[3d8] 3d 4s 4p

Hybridisations :
3d sp3 hybrid : Tetrahedral

[NiCl4]2– :

Cl– Cl– Cl– Cl–

(iv) Ni(CO)4 : Diamagnetic in nature. [Delhi 2012]

Ni (0) :
(3d84s2) 3d 4s 4p

Hybridisations :
3d

CO CO CO CO
sp3 hybrid Tetrahedral
Ni(Cl)4 :

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(v) [Ni(CN)4]2– : Square planar complex : Diamagnetic. [Delhi 2010, CBSE 2019, 2011]

Ni+2 ion :
(3d8) 3d 4s 4p

Hybridisation :
3d

d2sp2 : Square planar

[Ni(CN)4]2– :

CN– CN– CN– CN–

• [Mn(CN)6]3– : Magnetic moment of 2 electrons : d2sp3 : paramagnetic. [CBSE 2014]

[MnCl6]3– : Magnetic moment of 3 electrons : sp3d2

• [Fe(CN)6]3– :  = n(n + 2) = 1(1 + 2) : 1 unpaired electron : d2sp3

[FeF6]3– :  = 5(5 + 2) : 5 unpaired electron : High spin complex [sp3d2]

• [Co(C2H4)3]3– : Diamagnetic : d2sp3 : inner orbital complex. [CBSE 2017] [1M]

[CoF6]3– : Paramagnetic with four unpaired electron : sp3d2.
Limitation of VBT
1. It involves no. of assumptions.
2. It does not explain colour of coordination compounds.
3. It does not give explanation of kinetic and thermodynamic stabilities of complex.
4. It does not distinguish between week and strong ligands.

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Crystal Field Splitting in Octahedral Complexes

• Under the influence of 6 ligands degeneracy of d orbitals has been removed due to
ligand-metal electron repulsions in octahedral complex.

• Removal of degeneracy gives three orbitals [dxy, dyz, dzx] of lower energy (t2g) and
two orbitals of higher energy [d z 2 , d x 2 − y 2 = eg set].

• d
x2 − y 2
and d 2 orbitals point towards the axes along the direction of the ligand, will
z
experience more repulsion and will raised in energy.

• dxy, dyz, dzx orbitals are directed between axes, will be lowered in energy relative to
average energy (in the spherical crystal field).

• Splitting of degenerate levels due to the presence of ligands in a definite geometry

is called Crystal field splitting and the energy separation is denoted by Δo [Crystal
field splitting energy]. [CBSE 2011(C)] [2M]

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 d orbital splitting in an octahedral crystal field

• The extent of splitting depends upon the field produced by ligand and charge on
metal ion.
eg
d1 :
t2g
1
eg0

t2g

eg
d2 :
t2g
2
eg0

t2g
eg
d3 :
3
t2g eg0

t2g

[CBSE 2013] [3M]

(i) If 0 >P [ P = pairing energy ] (ii) If 0 <P

Now 4th electron enters into t2g orbital and Here, 4th electron enters in to one of eg
4 0
configuration = t2g eg orbitals giving the configuration t23 g e1g .

• Ligands for which 0 > P are known as • Ligands for which 0 < P are known as
strong field ligand. [SFL] weak field ligand. [WFL]

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Questions: (i) [CoF6]3– (ii) [Co(en)3]3+ (iii) [Co(NH3)6]3+

• F– as WFL

• en as SFL

• NH3 as SFL
Crystal Field Splitting in tetrahedral Complexes

• In tetrahedral coordination entity formation the d orbital splitting is inverted and is

smaller as compared to the octahedral field splitting.

14
 4
• For same metal and ligand :  t = 0
9
[ML6] → 0

[ML4] → t

t2g
[ML4] : d4 configuration
eg2 t2g
2

eg

COLOUR IN COORDINATION COMPOUNDS

• 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. For example if green is absorbed by the complex, it appears
red.

• Ti(H2O)6]3+ : Violet in colour eg eg

Transition
d1 : t2g
1
eg0 t2g t2g
1
Transition : t2g eg0 to t2g
0
eg1 Ground State Excited State

• In absence of ligand crystal field splitting does not occur and hence the substance
is colourless

(i) [Ti(H 2O)6 ]Cl3 ⎯⎯⎯
Voilet
→ colourless (TiCl3 )


(ii) CuSO4 .5H2O ⎯⎯
→ CuSO4 (colourless)

Limitations of CFT: From the assumptions that the ligands are point charges, it
follows that anionic ligands should exert the greatest splitting effect. But it is not true because
anionic ligands are found at the low end of spectrochemical series.
Bonding in Metal Carbonyls

• Compounds which have atleast one metal-carbon bond are called organometallic
compounds.

• The metal carbon bond in metal carbonyls possesses both σ and π character.

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• The M—C σ bond is formed by the donation of lone pair of electrons from the
carbonyl carbon to a vacant orbital of metal.

• The M—C π bond is formed by the donation of a pair of electron from a filled d-
orbital of metal into vacant π* orbital of CO.

• The metal to ligand bonding creates a Synergic Effect which strengthens the bond
between CO and the metal.
Stability of Co-ordination Compounds

• The stability of complex in solution refers to the degree of association between the
two species involved in the state of equilibrium.

• Equilibrium constant for the association expresses the stability

M + 4L ƒ ML4

Value of equilibrium constant  [ML4] 

• Stepwise stability constant: The equilibrium constant of each step of a complex

reaction is called stepwise stability constant. (k1, k2…) [CBSE 2011(C)] [2M]

• Overall stability constant: The equilibrium constant for net reaction (β4)

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 (i) M + L ƒ ML k1 = [ML] / [M][L]
(ii) ML + L ƒ ML2 k 2 = [ML2 ] / [ML][L]
(iii) ML2 + L ƒ ML3 k 3 = [ML3 ] / [ML2 ][L]
(iv) ML2 + L ƒ ML4 k 4 = [ML4 ] / [ML3 ][L]

M + 4L ƒ ML4 4 = [ML4 ] / [M][L]4

• Then → 4 = k1  k2  k3  k4

IMPORTANT PREVIOUS YEAR QUESTIONS

(i) What is meant by chelate effect? [CBSE 2015] [1M]

• When a didentate | polydentate ligand containing donor atoms positioned in such a

way that, they coordinate with the central metal ion forming a five or six
membered ring. The effect is called chelate effect.

• As a result of chelate effect, the stability of the complex increases.

NH
.. 2 NH
.. 2
.. M ..
NH2 NH2

(ii) Stability of complex : [COF6]3– < [Co(en)3]3+ [CBSE 2019] [1M]

(iii) CO is stronger complexing agent then NH3, why? [CBSE 2012] [1M]

• There exist a back bonding in CO complexes in which CO accepts electron density

from the filled a orbitals of metal atom into their orbital. So, there are as well as
interaction with metal in case of CO. But NH3 makes only bond with metal.
Therefore CO is a stronger completing agent then NH3.
(iv) Write the state of hybridization the shape and the magnetic behavior of following
complex entities. [CBSE 2011] [3M]
(a) [Cr(NH3)4Cl2]Cl [Cr(NH3)4Cl2]+1 Cr+3 d3
No pairing
happens

Cr+3 : Paramagnetic in nature due

3 to unpaired electrons
3d 4s 4p

[Cr(NH3)2Cl2]+ :

d2sp3 : Hybridisation
Octahedral

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(b) [Co(en3)]Cl3 [Co(en)3]+3 Co+3 d6

Pairing happens due

to presence of SFL (en
Co+3 ion :
3d0 4s 4p

[Co(en)3]3+ : : All electrons are paired

d2sp3 : Hybridisation Diamagnetic

Octahedral
(c) K2[Ni(CN)4] [Ni(CN)4]2+ Square planar / Diamagnetic

dsp2 : Hybridisation

[Delhi 2011, CBSE 2012] [1M]

(d) K4[Mn(CN)6] : IUPAC name : Potassium hexacyano maganate (II)
4(+1) + x + 6(–1) = 0 [Delhi 2011, CBSE 2010(C)] [3M]

Then x = + 2

(e) K4[Mn(CN)6] [Mn(CN)6]4– Mn+2 [Ar] 3d5

Mn+2 ion :
3d 4s 4p

[Mn(CN)4]4– :

d2sp3 : Octahedral : One unpaired electron

Paramagnetic

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