Coordination Compounds

Addition Compounds
When two or more than two simple salts are
allowed to chemically combine in a fix ratio then Concept Ladder
addition compound is formed.
On the basis of behaviour in aqueous solution The concept of coordination
they are of the following two types. compounds originates from
1. Double salt: - Addition compound in which teh tendency for complex
simple salts don’t loss their identity and its formation of transition
aqueous solution give test of its all constitute elements.
ions.
y Double salts loss their identity in aqueous
solution.

y All Alums are double salt.

2. Complex compound: - Addition compound in Rack your Brain
which simple salts loss their identity and it’s
aqueous solution doesn’t give test of its all
State whether the given
constitute ions.
complexes are double salt or
Coordination Compounds

y Complex compound don’t loss their identify

complex compound
in aqueous solution.
(i) K4[FeCN6]
(ii)[Link].2Na2SO4

1.
 Classification of Complex Compound
1. On basis of type of ligands
(i) Homoleptic complex: - Same type of ligands
Ex.

Concept Ladder

First coordination
compound is Prussian
(ii) Heteropoietic Complex: - Different type of
blue, which was accidently
ligands
prepared in 1704 by a Berlin
colour maker, prepared by
strong heating animal waste
and sodium carbonate in
an iron container.

2. On the basis of degree of dissociation

(i) Perfect complex compound : Relatively more
stable and its aqueous solution doesn’t give
test of its all constitutive ions.

(ii) Imperfect complex compound: - Relatively

less stable and its aqueous solution gives
test of its all constitute ions.
Coordination Compounds

2.
y Imperfect complex compound which
undergoes 100% ionisation is known as double Concept Ladder
salt.
y There is no sharp line between perfect and
d-Block metals have strong
imperfect complex compound.
complex forming tendency
y Complex forming tendency decreases down a
due to smaller size, high
group in s-block because size increases.
charge and presence of
vacant orbitals.
Representation of complex ion
Coordination sphere: -

Outside region: -
y Ionisation sphere
y Free ion
y Cation
Naming of ligands Definitions
y —O—suffix provided to the name of anionic
ligands. The neutral molecules; cations or
y —ium suffix provided to the name of cationic anions which are directly linked
ligands. with the centred metal atom
Anionic ligands ending with -ide are named by or ion in complex ion are called
replacing -ide with suffix -o or replacing -e by -o. ligands.

Ligands whose names end in -ite or -ate

become -ito or -ato, i.e., by replacing the ending
-e with -o.

Q.1 Green colour of leaves is due to presece of chlorophyll which is a complex

compound. Which metal is present in it?
Coordination Compounds

A.1 Magnesium

3.
 Classification of ligands
(a) On the basis of denticity Definitions
1. Monodentate ligand
(i) Neutral ligands The ligands that have one donar
H2O aqua PH3 Phosphene atom i.e. they only donate one
NH3 Ammine p(Ph)3 Triphenyl electron pair to central metal
phosphene atom or ion are known as
CO Carbonyl O2 Dioxygen monodentate ligands.
CS Thiocabonyl N2 Dinitrogen

NO Nitrosyl Pyridine(Py)

O
||
CH3NH2 Methyl Amine H N − C− NH
 Urea
2 2

Concept Ladder
H2N—NH2 Hydrazine
y Hydrozine never acts as bidentate ligand.
(ii) Cationic ligand: - Denticity of the ligands is
O2+ Oxygenium termed as the nubmer of
coordianting or ligating
+
NO Nitrosyliium groups present in a ligand.
Or Nitrosonium
H2N — NH3 Hydrazinium
(iii) Anionic ligands
F- Flurido S-2 Sulphido
Or fluro Or sulpho
Cl- Chlorido OH- hydroxide
Or chloro Or hydroxo
Br- Bromido CH3O– Methoxido
Or bromo Or methoxo Previous Year’s Questions
I- Iodido O2- Superoxido
Or Ido Or superoxol
Which of these cannot act as a
O-2 Oxido O2-2 Peroxido
ligand?
Coordination Compounds

Or peroxo
[AIPMT]
NO2- Nitro N-3 Nitrido
(1) NH3 (2) H2O
N3 Azido
-
NH2– Amido
(3) CO (4) NH4+
H- Hydrido

4.
2. Bidentate ligands
(i) Ethylene diamine (en) (ii) Propane 1,2–diamine
Or (ethane 1, 2–diamine) Or propylene diamine (Pn)

(iii) Dipyridyl (dipy) (iv) Oxalato (OX)-2

(v) Glycenato (gly)- (vi) Dimethyl glyoximato (dmg)-

3. Polydentate ligands
All bidentate and polydentate ligand are chelating
ligands.
No of chelate ring = Denticity – 1 Previous Year’s Questions
(i) Diethylenetriamine (dien)
Denticity = 3
The anion of acetylacetone (acac)
No. of rings = 2
forms Co (acac)3 chelate with Co3+.
Neutral
The rings of the chelate are
[NEET-2013]
Coordination Compounds

(1) five membered

(2) four membered
(3) six membered
(4) three membered

5.
 (ii) (trien) – Triethylene tetramine
Denticity = 4 Concept Ladder
Chelate rings = 3
Neutral
Chelating ligands form more
(iii) Terpyridine
stable complexes than the
Denticity = 3
unidentate analogs. This is
Chelate rings = 2
called chelating effect.
Neutral
(iv) Ethylenediamine tetracetato (EDTA)-4
2N 4(O)
Denticity = 6
Chelate rings = 5

Rack your Brain

Explain how dithicoxalate

behaves as ambidentate ligand.

(v) Ethylenediamine triacetato (EDTA)-3

Denticity = 5
Chelate rings = 4

4. Ambidentate ligands
y Ligands which have two different donor atoms
but at time of coordination such ligand can be
coordinate CMA by either of two donor atoms.
(a) (b)

Coordination Compounds

(c)

6.
5. Flexi dentate
Ligands which can change their denticity Concept Ladder
Ex. CO3−2 ,PO4−3 , SO4−2 , CH3 − COO− ,NO3− etc.
Coordination number
= S number of ligands
× Dentate character of
ligands

Ex. Co NH3

 ( )5 SO4  Cl
X+0−2 0
= X ⇒ +3

C.N ⇒ 6
5 by NH3 + 1 by SO4
Monodentate
(b) On the basis of e- donating and e- accepting
nature
1. Normal Or classical ligands
Ligands which only donate e- pair to CMA and Rack your Brain
form coordinate s bond.
Ex. NH2− , OH− ,N−3 , Cl − , O−2 Why CO is a stronger ligand than
2. Non classical or p acid or p acceptor ligands NH3 for many metals?
Ligands which donate e- pair to CMA and form
coordinate bond but simultaneously they accept
e- pair from CN through back bonding (synergic
bonding)
Ex. CO,NO+ , CN− , C6H6 , C5H5− , C2H4

Q.2 Why only transition metals are known to form p complexes?

Coordination Compounds

A.2 Transition metals/ions have empty d-orbitals into which the electron-pairs
can be donated by ligands containing p electron-pairs can be donated by
ligands contianing p electrons, i.e, electrons in their p moleculear orbitals, e.g.,
CH2=CH2, C5H5, C6H6 etc.

7.
 3. p donor and p acceptor ligand
Ligands which donate p e– to CMA and also Concept Ladder
accept e– density from CMA though synergic
bonding.
− As per VBT and MOT, it is
Ex. C6H6 , C5H5
implicit that the bond order
(i) of C—O bond decreases
but the C—O bond length
increases due to synergic
effect.

(ii)

Definitions

The number of atoms in a ligand

Coordination Number
that directly bonded to the central
Total no of e- pair accepted by CMA
metal atom or ion by coordinate
1. [Ni(dmg)2] = 4 bond is called coordination
2. [Pt(trien)]Cl2 =4 number of metal atom or ion.
3. [Fe(EDTA)] –
=6
4. [Co(en)2Ox]Cl =6
Some important points
1. Generally C.N of monovalent cation is two and
four except
− −3
( ) ( )
−
CN
Ex. Cu CN2  → Cu CN 
  excess  4 
O.S.=+1 C.N=
4
C.N=2
Previous Year’s Questions
2. Generally C.N of bivalent cation is four and six
Coordination Compounds

except. Coordination number of Ni in

+2 +2
Pt ,Pd  only 4 [Ni(C2O4)3]4– is
[AIPMT]
3. Generally C.N. of trivalent cation is six except
(1) 3 (2) 6
some exceptions.
(3) 4 (4) 2

8.
 4. C.N of tetravalent cation is 6.
5. C.N of CMA depends upon charge of CMA, Concept Ladder
six of CMA size of ligands and concentration of
ligand.
The effective atomic
Effective Atomic Number (EAN) number generally coincides
Total number of e- of CMA after accepting e- with the atomic number
pair from ligands of next inert gas in some
ENA = Z–(0.5) + 2 × C.N. cases.
1.
 ( )
6
( )
K4 Fe CN  ⇒ 26 − +2 + 2 × 6 ⇒ 36 [K]r
O.S. = +2, C.N. = 6
( ) ( )
2. K3 Fe CN  ⇒ 26 − +3 + 2 × 6 ⇒ 35 [Kr]
 6

O.S. = +3, C.N. = 6

3.

(
Fe η5 − C H
5 5 )  ⇒ 26 − ( +2) + 2 × 6 ⇒ 36 [Kr]
2

O.S. = +2, C.N. = 6

Sidgwick rule Rack your Brain
y If EAN of CMA in metal carbonyl is equal to
Atomic number of nearest inert gas then the
stability of metal is high. Calculate the EAN of the metal
−
atom in the following
(a)  ( )
Mn CO  < Mn CO  Stability
5  5
( ) (i) [Cr(CO)6]
= EAN 35
= EAN 36 (ii) [Ni(NH3)6]+

−
( ) ( )
−
  +e
→ V CO 
(b) V CO 6  
reduction  6
More stable
EAN 35= EAN 36

 ( )
(c) Fe CO  ⇒ neither oxidi sin g nor reducing
5

y Sidgwick rule is appliable only for metal

carbonyl.

Q.3 Write the coordination number and oxidation state of Platinum in the
Coordination Compounds

complex [Pt(en)2Cl2].

A.3 As en is bidentate ligand, coordination number of Pt = 6

x 0 −1
[Pt(en)2 Cl 2 ]
\ x – 2 = 0, x = +2
Oxidation state of Pt = 2
9.
 EAN Of Polynuclear Metal Carbonyl

(a)  5 ( )
2 Mn CO  
Dimer
→ Mn CO 
 10 
( )
= EAN 35= EAN 36

(b)  4
( )
2 Co CO  
Dimer
→ CO 2 CO 
 8 
( )
= EAN 35= EAN 36

FORMULA AND IUPAC NOMENCLATURE OF

COORDINATION COMPOUNDS
1. Formula of a Complex
(a) In formulas of both simple and complex salts,
cation precedes the anion. Nonionic compounds
are written as single units.
Concept Ladder
(b) Complex ions are written inside square
brackets without any space between the ions. In the old system, (i) the
(c) Metal atom and ligands are written in the ligands are named in the
order of negative, neutral
following order:
and positive without
(i) In the complex part, the metal atom is separation by hyphens.
written first followed by ligands in the (ii) when there are several
order, anionic → neutral → cationic. ligands of same kind, these
are listed alphabetically.
(ii) If more than one ligand of one type (anionic,
neutral or cationic) are present, then they
Coordination Compounds

are arranged in English alphabetical order,

e.g. between H2O and NH2, H2O should be
written first. Similarly, order of NO2-, SO32-
and OH– will be NO2−

10.
 (iii) When ligands of the same type have
similar name for the first atom, then the
ligand with less number of such atoms is
written first. Sometimes the second atom
may be used to decide the order. When
number of atoms are also same e.g., Out
Previous Year’s Questions
of NO2− , NH2− will be written first. In H3
•• ••
and N2 , NH3 will be written first as it The name of complex ion, [Fe(CN)6]3-
contains only one N-atom. is
[NEET-2015]
(iv) 
Polyatomic ligands and abbreviations for (1) hexacyanitoferrate (III) ion
ligands are always written in lower case (2) tricyanoferrate (III) ion
letters. e.g. (en), (py), etc. (3) hexacyanidoferrate (III) ion]
(4) hexacyanoiron (III) ion
(v) Charge of a complex ion is represented as
over script or square bracket.
Examples,
K4[Fe(CN)6] — First cation and then anion
[CrCl2(H2O)4] Br—Cl– (negative ligand) before H2O

Q.4 Write the formulae of the following:

(i) bis (acetylacetonato) oxovanedium (IV)
(ii) dichloridoplatinum (IV) tetrachloridoplatinate (II)

A.4 (i) [V (acac)2 O]

(ii) [PtCl2][PtCl4]

Q.5 Give the IUPAC names of the complexes

(i) K[BF4] (ii) [Fe(C5H5)2]
(iii) [Mn3(CO)12]
Coordination Compounds

A.5 (i) potassium tetrafluoridoborate (III)

(ii) bis (cyclopentadienyl) iron
(iii) dodecacarbonyl trimagnaese (0)

11.
 2. Nomenclature of Coordination Compounds
Mononuclear coordination compounds are
named by following these rules:
(a) In both the positively and negatively charged Rack your Brain
coordination compounds, the cation is named
first followed by the anion. Write the name for iron metal
(b) The name of the central atom/ion is written when it is used as complex
after the ligands are named in alphabetical order. anion?
(This procedure is reversed in writing its formula).
(c) Names of the anionic ligands end in –o.

(d) Names of neutral and cationic ligands are the

same except for aqua for H2O, ammine for NH3,
carbonyl for CO and nitrosyl for NO. These are
placed within parentheses ( ).
Coordination Compounds

12.
(e) Positive ligands are named as:
Concept Ladder

y Prefixes mono, di,

tri, etc. are used to
indicate the number of
the individual ligands
in a coordination
(f) Oxidation state of the metal in a cation, anion compound.
y When the names of
or a neutral coordination compound is indicated
the ligands include a
by a Roman numeral in parenthesis. numerical prefix, then
(g) When the complex ion is a cation, the metal is the terms, bis, tris,
tetrakis are used, and
named same as the element. For example, Co in
the ligand to which
a complex cation is called cobalt and Pt is called they refer is placed in
platinum. In an anion, Co is called cobaltate. For parentheses.
some metals, their Latin names are used in the
complex anions, e.g. ferrate for Fe.

(h) Nomenclature of a neutral complex molecule

is done in the similar way as that of a complex
cation.
The following examples illustrate the
Rack your Brain
nomenclature for coordination compounds:
• [Cr(NH3)3(H2O)3] Cl3 is named as:
Explain with an example how
Triamminetriaquachromium (III) chloride
the name of the metal differs
• [Co (H2NCH2CH2NH2)3]2 SO4 is named as: Tris in cation and anion even though
(ethane-1, 2-diammine) cobalt (III) sulphate they contain the same metal
• [Ag (NH3)2] [Ag(CN)2] is named as: Diamminesilver ions.
(I) dicyanoargentate (I)
Coordination Compounds

(i) Ligands which join two metals are known as

‘Bridge ligands’ and they are prefixed by ‘µ’ (mu).

E.g. , in this

complex.

13.
 3. Nomenclature of Complexes
(I) Cationic Complex
Concept Ladder
[Cr(NH3)3(H2O)3]Cl2
triamminetriaquachromium (III) chloride Polyatomic ligands are
(i) The number of the individual ligands are enclosed in parentheses
but all ligands are
indicated by prefix like mono, di, tri, etc. and
formulated without any
ligands are named in an alphabetical order.
space in between.
(ii) Central metal atom and oxidation state
indicated by Roman numeral in parenthesis.
(iii) Name of ionisable anion.
(II)Anionic Complex
K3[Fe(CN)6]
Potassium hexacyanoferrate (III)
Previous Year’s Questions
(i) Name of ionisable metal and oxidation state
(ii) Name of ligand in an alphabetical order The hypothetical complex
chlorodiaquatriammine cobalt (III)
(iii) Central metal atom + ate and oxidation state
chloride can be represented as
(III) Neutral Complex [AIPMT]
(1) [CoCl(NH3)3(H2O)2]Cl2
[Pt(NH3)2Cl(NO2)]
(2) [Co(NH3)3(H2O)Cl3]
Diammine chloronitrito-N-platinum (II) (3) [Co(NH2)3(H2O)2Cl]
(i) Name of ligands in an alphabetical order (4) [Co(NH3)3(H2O)3]Cl3

(ii) Central metal atom and oxidation states.

Q.6 Give the IUPAC names of the complexes

(i) K[BF4] (ii) [Fe(C5H5)2]
(iii) [Mn3(CO)12]

A.6 (i) potassium tetrafluoridoborate (III)

Coordination Compounds

(ii) bis (cyclopentadienyl) iron

(iii) dodecacarbonyl trimagnaese (0)

14.
Magnetic Nature
Ferromagnetic : Fe, Co, NO2
Concept Ladder
Spin magnetic moment = (m) = ( )
n n + 2 B.M.

n 1
= µ 1.73
= The magnetic property
n
= 2 =
µ 2.83 depends upon oxidation
n
= 3 =
µ 3.87 state of central metal atom
or ion and nature of ligand.
n
= 4 =
µ 4.90
n
= 5 =
µ 5.92

Spin magnetic moment of bivalent cation of 3d series

Spin magnetic moment of trivalent lanthanoids

y ‘Na’ (Neodymium) has max. M.M. among lanthanoids due to sum of spin magnetic moment
+ orbital magnetic moment.
Bonding in complex compound
1. Werner’s Theory
According to Werner, central metal atom has two types of valencies
Coordination Compounds

15.
 y All secondary valencies have specific
arrangement according to C.N. Concept Ladder
CN = 2 → Linear
CN = 3 → Trigonal planar
In 1898, Werner proposed
CN = 4 → Tetrahedral or square planar the concept of a primary
CN = 5 → TBP or square pyramidal valence and a secondary
CN = 6 → Octahedral valence for a metal ion.

 (
Co H O  Cl
2 6
)
3

O.S. ⇒ +3 CN = 6
Primary valency =+3
Secondary valency =6
Satisfied by 3Cl Satisfied by 6H2O

y Possible complex of CaCl3. 6H2O

O.S = +3 C.N. = 6 Rack your Brain

(a) Ca (H2O )6  Cl 3 = 4 ions

  Waht are the limitation of
( )
(b) Co H2O Cl  Cl 2 .H2O = 3 ions
 5 
Werner's theory?

(
(c) Co H2O
 )4 Cl2  Cl.2H2O = 2 ions
(
(d) Co H2O
 )3 Cl3  3H2O not possible
AgNO solution
y Pt Cl4. 4NH3 
3
→ 2 mol AgCl ppt
O.S = +4 C.N. = 6
[Pt(NH3)4Cl2]Cl2
Previous Year’s Questions
AgNO
y Pt Cl4. 2HCl  3
Solution
→ No. ppt
O.S = +4 C.N = 6 Which one of the following is an
H2 PtCl6  outer orbital complex and exhibits
paramagnetic behaviour?
Hexachloro platinic (IV) acid
[AIPMT-2012]
AgNO
y Pt Cl2. 4NH3  3
→ 2 mole AgCl ppt (1) [Ni(NH3)6]2+
Coordination Compounds

Solution
(2) [Zn(NH3)6]2+
O.S = +2 C.N. = 4
(3) [Cr(NH3)6]3+
[Pd(NH3)4]Cl2
(4) [Co(NH3)6]3+

16.
Valence Bond Theory
y Central metal atom releases e– according to
its O.S.
y Central metal atom will provide vacant orbitals
according to its coordination number.
y These vacant orbital undergo histrion and
form coordinate s bond with donor atoms.
y Hybridisation state of central metal atom Concept Ladder
depends upon C.N. and nature of ligand
According to VBT, the
M.M. dipole moment, isomerism etc. are also
atomic orbitals of the
helpful in hybridisation prediction.
metal ion hybridize to
C.N = 2 sp linear form hybrid with definite
C.N = 3 sp2 Trigonal planar directional properties.
C.N = 4 sp3 Tetrahedral There hybrid orbitals tend
dsp2 square planar to form strong chemical
C.N = 5 sp3d TBP bonds with the ligand
dsp3 (i) TBP orbitals.
(ii) Square pyramidal (dx2y2)
C.N = 6 sp3d2 Octahedral (SBP)
d2sp3 Octahedral (SBP)
y In presence of strong field ligand (SFL),
the pairing of (n-1)d e– is possible before
hybridisation but this pairing is not possible
in presence of WFL.

Rack your Brain

Coordination Compounds

y All ligands acts as SFL with 4d and 5d series

metal ions. Name the type of spin complex
y P- acts as SFL with Ni+4 involved for hybridisation of inner
y H2O and C2O4–2 acts as SFL with CO+3 (n – 1)d orbital.
y NH3 act as WFL with Fe+2 and Mn+2.
y H2O act as SFL with Cu+2 (C.N = 4)

17.
 −2

 ( )
(1) Ni CN 
4
Concept Ladder
O.S. = +2 C.N = 4 ligand = SFL
Ni = 3d84s2
The number of unapaired
electrons in the complex,
determins the geometry
of the complex as weel as
hybridization of the central
metal ion and vice-verse.

−2 −2

 ( )   (
(2) Ni Cl 4  or Ni SCN )
4 Rack your Brain
O.S = +2 C.N = 4 ligand = WFL
Ni = 3d84s2 Find the value of magnetic
moment for [CuCl4]-2.

Previous Year’s Questions

 ( )
(3) Fe CO  D.M. = 0
5

O.S. = 0 C.N. = 5 Ligand = SFL The geometry and magnetic

behaviour of the complex [Ni(CO)4]
are
[NEET-2018]
(1) square planar geometry and
diamagnetic
(2) tetrahedral geometry and
Coordination Compounds

diamagnetic
(3) square planar geometry and
paramagnetic
(4) tetrahedral geometry and
paramagnetic

18.
 −2
(4) MnCl 4  sp3
Concept Ladder
O.S. = +2 C.N. =4 Ligand = WFL

Under the influence of a

strong ligand, the electrons
can be forced to pair up
against the Hund's rule of
maximum multiplicity.

−3
(5) CuCl5  sp3d
O.S. = +2 C.N = 5 Ligand = WFL

Rack your Brain

Find hybridization of [Ni(CN)5]-3

compound.

−4

 ( )
(6) Ni CO  or Ni CN 
4  4
( ) sp3

O.S = 0 C.N = 4 Ligand = SFL

Previous Year’s Questions

Aluminium chloride in acidified

aqueous solution forms a complex
'A', in which hybridisation state
of Al is 'B'. What are 'A' and 'B',
respectively?
Coordination Compounds

[NEET-2019]
(1) [Al(H2O)6]3+, sp3d2
(2) [Al(H2O)4]3+, sp3
(3) [Al(H2O)4]3+, dsp2
(4) [Al(H2O)6]3+, d2sp3

19.
 (
(7) Fe H2O
 )5 (NO) SO4
O.S = +1 CN = 6 Ligand = WFL

( )
(8) NiCl 2 PPh3  Paramagnetic
 2

O.S = +2 CN = 4 Ligand = WFL = No pairing

Previous Year’s Questions

Pick out the correct statement

with respect to [Mn(CN)6]3-
[NEET-2017]
( )
−2 −
(9) RhCl PPh  , PdCl 4  , AgF4  (1) It is sp3d2 hybridised and
 3 
tetrahedral
C.N=4
Rh+ ,Pd+2 , Ag=
+3
4d8 
SFL
→ dsp2 (2) It is d2sp3 hybridised and
octahedral
(3) It is dsp2 hybridised and square
planarl
(4) It is sp3d2 hybridised and
octahedral
Coordination Compounds

20.
 −2
(10) NiF6  Ni+4 → F−act as SPL
Concept Ladder
O.S. = +4 CN = 6

Pt(II) and Au(III) always form

square planar complexes
irrespective of their ligands
being strong or weak.

( )
−4


( )
(11) Fe CN O2− 
5 
O.S. = +2 CN = 6 Ligand = SFL

Rack your Brain

What is the shape of [Co(NH3)6]+2

compound?
−2

 ( )
(12) Fe CO 
4

O.S. = –2 CN = 4 Ligand = SPL

Previous Year’s Questions

A magnetic moment at 1.73 BM

will be shown by one among the
Coordination Compounds

Drawbacks of VBT following options

(1) It can’t explain stability of complex compound [NEET-2013]
(2) It can’t explain colour of complex compound (1) TiCl4 (2) [CoCl6]4-
(3) It can’t explain d e- transference (3) [Cu(NH3)4]2+
(4) [Ni(CN)4]2-
(4) It can’t explain pairing of (n-1)d e–
(5) It doesn’t give any criteria for classification of SFL and WFL.

21.
 CFT for octahedral complex
dxy , dyz , dzx  t 2g Concept Ladder
dz2 , dx2  y2  eg
CFT is an electrostatic
model which considers
the metal ligand bond to
be ionic occuring purely
due to the electrostatic
interaction between the
metal ion and the ligand.

Q.7 Define crystal field splitting energy. On the basis of crystal field theory, write
the electronic configuration for d4 ion if D0 < P.

A.7 In a free transition metal ion, all the five d-orbitals are degenerate but when
it is involved in a complex formation, the degeneracy is split into two sets of
d-orbitals. This is called crystal field splitting.
The difference of energy between the two sets of d-orbitals is called crystal
field splitting energy (CFSE).
Coordination Compounds

The lower energy set of three d-orbitals is called t2g and the higher en-
ergy set of two d-orbitals is called eg. The three electrons first enter into
t2g, one in each orbital. If D0 < P, the 4th electron will enter eg. Hence, the
configuration will be t32g e1g.

22.
23.
Coordination Compounds
 Dn system
Electronic configuration of (n–1) de- of CMA Concept Ladder
(after splitting) depends upon 2 type of energies
are :
(1) D0(2) Pairing energy (P) Complexes possessing
There are two conditions d0 or d10 configuration of
(1) In presence of SFL D0 > P a metal ion are always
(2) In presence of WFL D0 < P diamagnetic.

Rack your Brain

Explain how d-d transition is

responsible for the colour of
transition metal complexes?

Concept Ladder

Complexes like CrO42-,

CrO72- and MnO4- have d0
configuration of the metal
ion but still exhibit intense
Coordination Compounds

colour. Here the colour

is caused by the charge
transfer spectra (CT) and
not by the d-d transition.

24.
Hybridisation State and Magnetic Nature
Concept Ladder

It is observed that the

higher the charge on the
central metal atom (or
oxidation state), higher is
the value for CFSE.

Configuration of metal in

Rack your Brain

Write the assumption made for

Crystal Field theory?

Factor affecting splitting energy

(1) 0  charges of central metal atom
(2) 0  Zeff of central metal atom

→ 5d series Zeff ↑
∆0 ↑ ∆0 ↑
3d  → 4d Series 
30 −50% 30 −50% 
(3) 0  strength of ligand
Previous Year’s Questions
(4) Geometry of complex
Coordination Compounds

∆sp > ∆0 > ∆ t The crystal field stabilisation

energy (CFSE) for [CoCl6]4- is 18000
4 ∆ cm-1. The CFSE for [CoCl4]2- will be
∆t = 0
9 [NEET-2019]
(1) 6000 cm-1 (2) 16000 cm-1
(3) 18000 cm-1 (4) 8000 cm-1

25.
 Examples,
+2 +3
(i) Co H2O ( ) (
< Co H2O  ) ∆0 Concept Ladder
 6  6
(I) (II)
Complexes normally exhibit
H2O acts as strong ligand with Co+3, so splitting
two kinds of stabilities
energy for (II) is higher than (I)
viz. thermodynamic and
+3 +3 +3
(ii) Fe (H2O )6  (
< Ru H2O 
 6
) (
< Os H2O 
 6
) ∆0 kinetic.
y Thermodynamic
Fe is a 3d series element whereas Ru and stability deals with
Os are 4d and 5d transition elements, so H2O is the metal-ligand
weaker ligand but it acts as strong ligand with bond energy, stability
higher d series transition element. constants etc that
+3 −3 affect the equilibrium.
(
< Cr NH3 ) 6  ( )
−3
(iii) CrCl6  < Cr CN  ∆0 y Kinetic stability deals
  6
with the rates of
Ligand strength for CN- > NH3 > Cl- reaction of complexes
(iv) NiCl 4 
−2
> NiCl6 
−4
in a solution.

(I) (II)
(I) is tetrahedral and (II) is octahedral complex
 t  o
Stability of complex compound
K
Mn  xL 

[MLx ]
MLx 
( formation constant ) K = x
M+n  L− 
   Previous Year’s Questions

K ↑, stability ↑
Crystal field splitting energy for
Stability ∝ charge of CMA high spin d4 octahedral complex is
∝ Zeff of CMA [NEET-2013]
∝ Strength of ligand (1) – 1.2 D0 (2) – 0.6 D0
∝ chelation effect (3) – 0.8 D0 (4) – 1.6 D0
Coordination Compounds

1
∝
size of CMA
Stability order :
−4 −3
(1) Fe CN 
 6
( )  ( )
< Fe CN 
6

O.S = +2 O.S. = +3

26.
(2)
+3 +3 +3

 2(
Co H O 
6
)  (
< Rh H2O 
6
) (
< Ir H2O 
 6
) Zeff ↑

(3)
+2 −4
( )6  ( )
−4
NiCl6  < Ni NH3 < Ni CN  ligand strength
  6

+3 −3 −
(4) Fe (NH3 )6   ( )
< Fe OX 
3
(
< Fe EDTA 
  )
Concept Ladder
No chelation 3 chelate 5 chelate rings
−3 −3
(5) Fe Ox 
 3
( ) ( )
< Fe CN 
 6
Weak ligands favor high
spin complexes because
Chelation synergic bonding they cannot pair up the
(6) Irving williams series electrons against Hund's
Mn+2 < Fe+2 < Co+2 < Ni+2 ≤ Cu+2 > Zn+2 rule while strong ligands
favor low spin complexes.
C.F.S.E. (Crystal field stabilisation energy)
Extra stabilisation (released energy) due to
splitting in comparison to no splitting

Q.8 Calculate CFS for the given compound :

−4
Fe ( CN) 
 6

A.8 ( )
Fe CN 
 6
−4

Priority to 2P = N, New pairs

Coordination Compounds

CFS = -0.4D0 × 6 +0.6D0 × 0

= -2.4 D0
Total pairs

27.
 CFSE = 0.4D0 nteg + 0.6 D0 nteg + xp = new pairs
CFT for Tetrahedral complex

Colour
(a) d-d Transition
y Colour of complex compound is due to d-d transition
y Ag. Solution of Ti+3 is violet .

y Colour of complex compound depends upon

spilitting energy.
Coordination Compounds

Rack your Brain

y Complex become colourless in absence
of ligand filled (no ligand, no splitting, no
transition) What is the difference between
y Colour of f-block compounds is due to f-f inner and outer orbital
transition. complexes?

28.
Examples,
(a) [Ti(H2O)6]+ become colourless on heating due Concept Ladder
to removal of water molecules.
(b) Anhydrous CuSO4 is colourless but hydrated In many complexes the
CuSO4 is blue (test of moisture) d-orbital split takes place
Anhyd. CuSO4 
+5H2O
 (
→ Cu H2O  SO4H2O
4
) in the two sets t2g and eg,
Colourless Blue vitriol which possess diferent
(b) Charge transfer energies. the difference
Colour of some compound is due to charge in energies of t2g and eg
transfer (e- transition) from anion to metal ion. lies in the visible region
of the spectrum and their
helps tramsition metal
KMnO4 purple 
  +3 +6
complexes to absorbe
K2Cr2O7 Orange  Mn or Cr = 3d° color.
Na CrO
 2 4
Yellow

(
 no d − d transition )
CrO2Cl 2 Blood Re d

(c) Polarisation
y Colour of same compound can be explained
on the basis of polarisation.
y Polarisation increase, possibility of finding
colour increase
Examples, Rack your Brain
(1) AgF coloulress but AgI yellow.
(2) PbF2 colourless but PbI2 yellow. Why SnF4 is colourless besides
(3) HgF2 colourless but HgI2 Red. SnI2 is red in colour?
(4) ZnS colourless but Cds yellow. HgS Black

Q.9 On the basis of crystal field theory, write the electronic configuration for d4
ion if D0 > P.
Coordination Compounds

A.9 In this case, the 4th electron will enter into t2g, i.e., pairing in one of the t2g
orbitals will take place. Hence, electronic configuration will be t2g4.

29.
Coordination Compounds

30.
Structural Isomerism
y Same molecular formula but different
structural formula
(1) Coordination Isomerism
It arises due to exchange of ligands between
complex cation and complex anion.

Q.10 How many Coordination isomers are there in the given compounds?
(a) Co (NH3 )  Cu (NO2 )  (b) Pt (NH3 )  PtCl 4 
 6 6  4 

 ( )3
(
(c) Co en  Cr NO2 ) 6


(d) Pt (NH3 )  ZnCl 4 
 4 

A.10 (a)

(b)
Coordination Compounds

31.
 (c)

(d)

(2) Ionisation Isomerism

y Structural isomer which give differ ions in
aqueous solution
y Ionization isomerism is the result of the Previous Year’s Questions
exchange of groups or ions between the
coordinating sphere and the ionization sphere.
The type of isomerism shown by
Examples,
the complex [CoCl2(en)2] is]
(a)
[NEET-2018]
(1) geometrical siomerism
Coordination Compounds

(b) (2) coordination isomerism

(3) ionization isomerism
(4) linkage isomerism

32.
(3) Hydrate Isomerism
y It is a special type of ionisation isomerism in Concept Ladder
which number of water molecules differ in
coordination sphere/outside region.
Complexes of formula MA2B2
Examples,
and MA2BC types have two
geometrical isomers, where
as MA4, MA3B and MAB3
do not show geometrical
isomerism when A & B are
monodentate ligands.
(4) Linkage Isomerism
y It arise due to presence of ambidentate ligand.
Examples,
[Co(NO2)(NH3)5]Cl2
Pentaamminenitrocobalt (III) chloride
(5) Polymerisation Isomerism
y Complexes which have differ molecular
formula but have same empirical formula. It Rack your Brain
is not a true isomerism.
Example, Can in a complex compound
[PtCl2(NH3)2] and [Pt(NH3)4][PtCl4] water molecules behave in two
ways? Explain in brief.

Geometrical Isomerism in square planar com-

plexes
y Tetrahedral complexes don’t show
‘Geometrical Isomerism’.
y Square planar complexes can show
‘Geometrical Isomerism’.
Previous Year’s Questions
y Any two identical ligands at 180° show Trans.
y All identical ligands at 90° show Cis.
The complexes [Co(NH3)6][Cr(CN)6]
Examples,
and [Cr(NH3)6][Co(CN)6] are
 (
(1) Pt NH3 )4  Cl2 Pt=
+2 C.N=4
5d8  → dsp2 the examples of which type of
Coordination Compounds

sq. planar
Ma4 
±
isomerism?
[NEET-2011]
( )
±
(2) Pt NH3  Cl = Ma3b (1) Linkage isomerism
 2
(2) Ionization isomerism
(aa) (ab) No G.I.
(3) Coordination isomerism
(4) Geometrical isomerism

33.
 (
(3) Pt NH3
 )2 Cl2  ⇒ Ma2b2 
(aa) (bb) (ab) (ab) Concept Ladder

Complexes of type MA4R2

exist in cis and trans
forms and both forms are
optically inactive due to
Is [Pt(NH3)2Cl2 B] — it is used as anticancer agent. plane of symmetry wherre
( )
(4) Pt NH3 Cl Br  ⇒ Ma2bc  2GI
 2 
as complexes of type
MA3B2 exist infacial and
(aa) (bc) (bc) (ac)
meridonial form but both
Trans cis
are optically inactive.

(5) 
( 3 2 )(  )
Pt NH H O Cl Br  ⇒ Mabed 3GI
 
( )
ab (cd), (ac) (bd), (ad)(bc) 2cis+1 trans

y Geometrical and Optical Isomerism in

octahedral complexes
(
(1) Co NH3
 )6  Cl3
±
Ma6  optically inactive
Previous Year’s Questions
(aa) (aa) (aa) No GI
The complex, [Pt(py)(NH3)BrCl]
(
(2) Co NH3
 )5 Cl  Cl2 will have how many geometrical
±
Ma5b isomers?
[NEET-2011]
(aa) (aa) (ab) No GI
(1) 3 (2) 4
(3) Pt NH
( )4 Cl Br  SO4
Coordination Compounds

 3 (3) 0 (4) 2
±
Ma4bc  2GI
(aa) (aa) (bc) (aa) (ab) (ac) O-inactive

34.
 ±

 ( )   ( )
(4) Pt en Cl 4  ⇒ M AA a4 

Rack your Brain

How many geometrical isomers

are possible for the [Ni(NH3)4]+2?

 ( )   ( )
(5) Pt en Cl 2Br2  = M AA a2b2 


GI = 3
O-active = 3
S.I = 4

±
( )2 ab
(6) M AA


Coordination Compounds

35.
 Application of Complex compound
(1) Test of Ni+2
NH4OH
Ni+2 + 2dmg → Ni dmg 
 2
( )

+2 CN=4 Rack your Brain

Ni= 3d8 
SFL
→ dsp2 , square planar diamagnetic

Explain in brief how by forming

complexes, silver and gold can
be extracted from metals.

(2) Test of Fe+2, Fe+3 and Cu+2

Coordination Compounds

(3) Test of sulphide ion

( )5 (N+O) → Na4 Fe (CN)5 (NOS)

Na4 S + Na2 Fe CN

Sodium nitroprusside Voilet / Brown colour

S−2 + N+ O → NOS

36.
(4) Separation of hydroxides or oxides

(5) If excess amount of KCN is added into CuSO4

solution then insoluble CuCN is formed which
later into soluble complex.
(6) AgCl or AgBr ppt (not AgI) are soluble in NH3 or
NH4OH
+
AgCl + 2NH3 → Ag NH3
ppt  ( )2  Cl −
soluble complex
Concept Ladder
(7) [EDTA]–4 is used for estimation and removal of
hardness of H2O.
Light blue colour of aq.
−2
Ca +2
+ EDTA −4
(
→ Ca EDTA 
  ) solution of CuSO4 term
into dark blue in presence
(8) Wilkinson catalyst [RhCl(PPh)3] is used for hy- of ammonia or NH4OH but
drogenation of alkene. in presence of acid there is
(9) Biological importance: - no colour change.
(a) Chlorophyll → Mg
(b) Vit–B12 → Co
(c) Carboxypeptide → Zn
(d) Plastocynin → Cu
(e) Insolin → Zn
(f) Haemoglobin → Fe+2
(g) Hyoglobin → Fe+2

Q.11 Describe with an example of each, the role of coordination compounds in :

(i) Biological system (ii) Analytical chemicstry
Coordination Compounds

(iii) Medicinal chemistry

A.11 (i) Vit. B-12, it is a antipernicious anemia factor.

(ii) Determining and estimation of metal
(iii) EDTA is used in lead poisoning.

37.
 Organometallic Compound
Compounds in which carbon atom of
hydrocarbon part is directly bonded with metal
or metalloid. Definitions
OMC Not OMC
R-MgX Cu3–COO–Na+ The compounds in which carbon
R-Zn-R C6H5O-Na+ forms a bond with an atom
Frankland reagent CaCO3 (metal/non-metal) which is less
R–Cd–R CaC2 electronegative than carbon, then
(Cu3)3As NaCN the compound as organometallic
(R2SiO)n Ti(OC6H5)4 compound.
[Ni-(CO)4]
Types
(1) s Bonded OMC
(C2H5)4Pb T.E.L used as anti knocking agent
[TiCl4 + (C2H5)3 Al] Ziggler natta catalyst (Het-
erogenous catalyst) = used for polymerisation of
alkene.
(2) p Bonded OMC Rack your Brain
Presence of p donor ligand

 ( 6 6 )
2
 
(
Cr η6 − C H  , Fe η5 − C H
5 5 ) 
2
Why compounds like alkoxides,
carbides and cyanides are
(3) s and p bonded OMC not termed as organometallic
Presence of synergic bonding compounds?

 ( )4 
( )
Ni CO  . Fe CO 
5

Trans effect

( )
K PtCl 3 η2 − C2H4 
 
+2 CN=4
Pt= 5d8  → dsp2
square planar diamagnetic Previous Year’s Questions
John Taller effect
Distortion in octahedral geometry due to un- An example of a sigma bonded
symmetrical e– cloud in eg set of orbitals.
Coordination Compounds

organometallic compound is
[NEET-2017]
(1) Grignard's reagent
(2) ferrocene
(3) cobaltocene
(4) ruthenocene

38.
Q.12 A coordination compound CrCl3.4H2O precipitates silver chloride when
treated with silver nitrate. The molar conductance of its solution corresponds
to a total of two ions. Write the structural formula of the compound and name
it.

A.12 The structural formula will be [Cr(H2O)4Cl2]Cl.

Tetraaquadichlorido chromium(III) chloride is the name of this compound.

Q.13 Why are low spin tetrahedral complexes not formed?

A.13 The crystal field splitting energy of tetrahedral complexes is too low. It is lower
than pairing energy so, the pairing of electrons is not favoured and therefore
the complexes cannot form low spin complexes.

Q.14 Explain why [Fe(H2O)6]3+ has a magnetic moment value of 5.92 BM whereas
[Fe(CN)6]3– has a value of only 1.74 BM.

A.14 H2O is a weak field ligand for [Fe(H2O)6]3+, won’t cause pairing of electrons,
therefore there are 5 unpaired electrons. CN- is a strong field ligand for
[Fe(CN)6]3– so, Fe3+ has six unpaired electrons which will cause pairing of all
the electrons. So, the electrons will start pairing leaving behind one unpaired
electron.

Q.15 Name the type of isomerism when ambidentate ligands are attached to a
central metal ion. Give two examples of ambidentate ligands.

A.15 Ambidendate ligands are those having different two binding sites.
Coordination Compounds

Examples: Isothiocyanato Thiocyanato and Nitrite-N Nitrito-O

The type of isomerism when ambidentate ligands are attached to a central
metal ion is called linkage isomerism because they only differ in the atom that
is linked to the central metal ion.

39.
 Q.16 CuSO4.5H2O is blue while CuSO4 is colourless. Why?

A.16 In CuSO4.5H2O, H2O molecule is a ligand. Whereas, in CuSO4, there are no

H2O molecules to act as ligands, so no crystal field splitting happens and for
CuSO4.5H2O as electrons will excite to higher d-orbital and show colour.

Q.17 Why do compounds having similar geometry have a different magnetic

moment?

A.17 They differ in the number of paired and unpaired electrons. A strong field li-
gand will cause pairing of electrons while a weak field ligand will not cause
pairing. Pairing or not pairing will change the number of unpaired electrons,
which affects the magnetic moment.

Q.18 Why are low spin tetrahedral complexes not formed?

A.18 For tetrahedral complexes, the crystal field splitting energy is too low. It is
lower than pairing energy so, the pairing of electrons is not favoured and
therefore the complexes cannot form low spin complexes.

Q.19 Based on crystal field theory explain why Co(III) forms a paramagnetic
octahedral complex with weak field ligands whereas it forms a diamagnetic
octahedral complex with strong field ligands.

A.19 The electronic configuration will be t42g e2g. It has 4 unpaired electron and
paramagnetic. With weal ligand Δ0 < p. The configuration with strong field
Coordination Compounds

ligand will be t62g e0g. the Δ0 > p and there won’t be any unpaired electron
therefore diamagnetic.

40.
Summary

y In coordination compounds - central atom acts as lewis acid and ligands act as
lewis base.
y Trans isomer does not show optical isomerism due to presence of symmetry. Only
Cis isomer show optical isomerism due to presence of unsymmetry.
y Geometrical isomerism is not possible for complexes of type MA4 and MA3B.
y MA2X2Y2 type of complexes show both optical and geometrical isomerism.
y (i) Octahdral complexes of type MA3B3 from 2 isomeric forms.
(ii) Octahedral complexes of type MABCDEF from 15 isomeric forms.
y CO, CN– and NO2– ligands cause passing of e– in central metal atom.
y Zeisse's salt K[PtCl3(h2–C2H4)]
Ferrocene [Fe(h2–C2H5)2].
y Cis platin – cis [PtCl2(NH3)2] is used in treatment of cancer.
y (i) Zegler - Natta Catalyst is (PH3P)3RhCl is use in hydrogenation of alkenes.
(ii) Wilkinson's catalyst (Ph3P)3RhCl is used in hydrogenation of alkenes.
y Bleaching powder is mixed salt – CaOCl2 Ca2+ + Cl- + OCl-.
y Effectifve atomic no. (EAN rule) by Sidgwick :
EAN = Z – (O.N.) + 2 × (C.N.)
where Z = At. no. of central atom.
O.N. = Oxidation no. of central atom.
C.N. = Co-ordination of central metal atom.
y EDTA is hexadentate ligand — It has six donar atoms; 2 nitrogen atoms and 4
oxygen atoms.
y CO is called p acid ligand due to back bonding present in it.
y In CuSO4.5H2O (solid), Copper is co-ordinated to 4 water molecules.

Coordination Compounds

41.