INORGANIC CHEMISTRY

NOTES

COORDINATION
COMPOUNDS
PART 1

strong strong
wild base Griffon
eg fear 5M KAREN 6
α
d Kmetal complex
cation N c
done
 COORDINATION COMPOUNDS (COMPLEX SALTS)

Molecular/Addition Compound

Double salt Complex salt

Ions in aqueous solution do Ions in aqueous solution may
not lose their identity lose their identity

Molecular/Addition compound :
When two or more simple salts are allowed to chemically combine together in a fixed proportion by weight,
then molecular/addition compounds are formed, depending upon their behaviour in aqueous solution they are
classified into two types of salts named as double salts and complex salts.

Double salts :
Molecular/addition compound in which individual components don’t lose their identity and aqueous solution
gives positive test of all constituent ions is called double salt.
cool Water
1. FeSO4 + (NH4)2SO4+ 6H2O FeSO4.(NH4)2SO4.6H2O Fe2+(aq) +2 NH+4 (aq)+ 2SO2–
4
(aq)+ 6H2O
(Simple salt) (Simple salt) Mohr’s salt green colour
(Light green crystals)

cool
2. KCl + MgCl2 + 6H2O KCl.MgCl2.6H2O Water K+(aq) + Mg2+(aq) + 3Cl–(aq) + 6H2O
Carnallite

cool
3. K2SO4 + Al2(SO4)3 + 24H2O K2SO4.Al2(SO4)3.24H2O
(Simple salt) (Simple salt) Potash Alum (Double salt)
(white crystalline solid)

Water

2K+(aq) + 2Al3+(aq) + 4 SO24 – (aq) + 24H2O ( )

Some important points about Alums :

Empirical formula of Alum : M M(SO4)2.12H2O
Molecular formula of alum : M2SO4.M2(SO4)3.24H2O or M2M2(SO4)4.24H2O
where M = Monovalent cation like NH+4 and all s-block alkali metal cations except Li+ cation.
M = Trivalent cation like Al3+, Fe3+, Cr3+ etc.
Naming of Alums :
K2SO4.Al2(SO4)3.24H2O - Potash Alum
Na2SO4.Al2(SO4)3.24H2O - Soda Alum
(NH4)2SO4.Al2(SO4)3.24H2O - Ammonium Alum
M'2SO4.Fe2(SO4)3.24H2O - Ferric Alum
K2SO4.Fe2(SO4)3.24H2O - Potassium Ferric Alum
Na2SO4.Fe2(SO4)3.24H2O - Sodium Feric Alum
(NH4)2SO4.Fe2(SO4)3.24H2O - Ammonium Ferric Alum
M'2SO4.Cr2(SO4)3.24H2O - Chrome Alum.

PILS
Complex salts :
Molecular Addition Compound in which individual components may lose their identity and its aqueous solution
doesn’t give positive test of all its constituent ions is called complex salt.

1. Formation of Potassium Ferrocyanide K4[Fe(CN)6]

Kf > Ksp +2 4–
Water + 4–
Feebly ionize
2+ –
Fe(CN)2+ KCN K4 [Fe(CN)]6 4K (aq)+[Fe(CN)]6 Fe (aq) + 6CN(aq)
Simple Simple Eqb. shift forward Potassium (Ferrocyanide ion) Low conc. is not
salt salt Ferrocyanide sufficient for +ve test
(Complex anion) 2+
of Fe
2. Formation of Potassium Ferricyanide ion K3[Fe(CN)6]
Kf > Ksp 3+ Water Feebly ionize
3+ 3+ –
Fe(CN)3 + KCN K3[Fe(CN)]6 +
3K (aq) + [Fe(CN)]6
3–
Fe (aq)+6CN(aq)
Simple Simple Eqb. shift forward Potassium (Ferricyanide ion) Low conc. is not
salt salt Ferricyanide
sufficient for +ve test
(Complex anion) 3+
of Fe
Type of complex salts :
On the basis of degree of ionization of complex ions/salts can be classified into two types.
• Perfect complex salt
• Imperfect complex salt

Perfect complex salts :

These complexes are stable enough and their aqueous solution don’t give positive test of all constituent ions
due to negligible degree of ionization of their complex ions.
I Kf > Ksp 1+
3–
CuCN + KCN K3[Cu(CN)]4 Water 3K+(aq) + [Cu+1(CN)4]3–(aq)
White ppt. Simple Eqb. shift Complex salt
(Simple salt) salt forward (perfect complex
salt w.r.t H2S)
Feebly
into
+
2Cu (aq.) dispn. 2+
Cu (aq) + Cu
CCN 41 ionise reaction

H2S gas 2+
no ppt of CuS Cu (aq) + 4CN
2+ 2–
[Cu ][S ] < Ksp Very low
concentration
Imperfect complex salts :
These complexes are relatively less stable and their aqueous solution give positive test of all constituent ions
due to appreciable degree of ionization of complex ion.

Kf > Ksp
Cd(CN)2 + 2KCN K2[Cd(CN)4]
Eqb. shift
White ppt (Simple salt) forward (Imperfect salt w.r.t H2S and
(Simple salt) perfect w.r.t HCl)
Water
+ – Feebly 2+ 2– +
Cd (aq) + 4CN [Cd (CN)4] + 2K (aq)
Ionise
Low concentration

H2S gas
(reagent)
CdS (yellow ppt)
2+ 2–
[Cd ][S ] > Ksp
ie imperfectcomplex
v r't Mrs
HCl gas
(reagent) No ppt (CdCl2 is water soluble salt)
perfectcomplex
2+ – 2
[Cd ][Cl ] < Ksp
w 8 t Hcl
 From above discussion, it is clear that perfect and imperfect nature of the complex salt not only depends
upon degree of ionisation of complex ion but also depends upon the nature of the reagent used for precipitation
of salt (Ksp of precipitated salt).

ut
y
Conclusion :
1. If aqueous solution of molecular addition compound gives +ve test of all its constituent ions and also give +ve
test of additional complex ion then it is called imperfect complex salt w.r.t reagent used.

2. If aqueous solution of molecular addition compound doesn’t give +ve test of all constituent ions and gives +ve
test of additional complex ion is called perfect complex salt w.r.t reagent used.

3. If aqueous solution of molecular addition compound gives +ve test of all constituent ions and never gives +ve
test of any additional ion then it is called double salt.

Classification of complex salts on the basis of their composition : Complex salts are classified into four types

1. Complexes having simple cation and complex anion.

K+[Ag(CN2)]–, K +3 [Fe(CN)6]3–, K +4 [Fe(CN)6]4–, K +2 [CuCl4]2–
2
2. Complexes having complex cation and simple anion. 17 CN 4
[Cu(NH3)4]2+ SO2–
4
, [Ag(NH3)2]+Cl–, [Co(H2O)6]2+ Cl2–
2
, [Ni(NH3)6]2+ SO2–
4 8 4 INE
3. Both cation and anion are complex.

244

2
 2
2–
 44

2
 2 2 2
2–
  33
2
2 2ZnCl
2
2
2–

 Pt(NH )
3 4 
a  Pt Cl 4  , Pt
2 12
 Cl2 (NH3 )4   Pt Cl 4  , Cr
1 1
Cl(NH3
)5   4


4. Neutral or molecular complexes.

f
[Fe(CO)5]0 , [Ni(CO)4]0 , [Cr(CO)6]0  M(CO)x (Neutral metal carbonyl complexes)

Classification of complex salts on the basis of type of ligands around CMA/ion.

Homoleptic complex  metal surrounds by same type of ligands

K +4 [Fe(CN)6]4–, [Ag(NH3)2]+Cl–, [Co(H2O)6]2+ Cl2–
2
, [Ni(NH3)6]2+ SO2–
4

Heteroleptic complex  metal surrounds by different type of ligands

2 3 2
PtCl2  NH3  
 4
, Co  H2O 3  NH3 3  , CrBr  NH3 5  , Ni NH3 4 Cl2 

Representation of complex ion :

n±
[MLx] ionization sphere

coordination
sphere

where M : Central metal atom/ion (usually d-block cations)

L : Surrounding ligands (Lewis base)
x : Total number of surrounding ligands
n ± : (+ve) or (–ve) unit charge on coordination sphere.
Outside region apart from coordination sphere is called ionization sphere.
Ligand : Electron rich species which can donate one or more electron pairs (.p. or -electron pair) to the vacant
orbital of central metal atom/ion is called ligands.

Classification of Ligands

(I) (II) (III )

On the basis of charges On the basis of Denticity –
On the basis of e pair donating &
- Negative ligands - Mono/Unidentate ligands accepting tendency
 L)
- Classical (normal) lignads (M
- Neutral ligands - Bi/Didentate ligands
- Poly/Multidentate ligands 
- Positive ligands - Non classical (-acid) ligands(M  L)
- Ambidentate ligands
(Must be –ve ligand)

Negative Ligands : Carry negative charge E.EE EE9

– – –
H : Hydride SCN : Thiocyanate CH3COO : Acetate
– –
F : Flouride NCS : sothiocyanate C2O4
2–
: Oxalate
– 2–
Cl : Chloride SO4 : Sulphate
and
2–
– 2–
CO3 : Carbonate
Br : Bromide SO3 : Sulphite –
I
–
: Iodide 2–
CH3 : Methyl
S2O3 : Thiosulphate –
O2
2–
: peroxide –
CH3CH2 : Ethyl
N3 : Azide –
O2
–
: Superoxide 3–
C6H5 : Phenyl
2– N : Nitride SnCl3
–
: Trichlorostannite
O : Oxide NH2
–
: Amide –
– C5H5 : Cyclopentadienyl
OH : Hydroxide NH
2–
: mide
– –
CH3O : Methoxide – CH2 = CH – CH2 : Allyl
NO2 : Nitrite
(I) On the Basis of charges

–
OCN : Cyanate NO3
–
: Nitrate
–
NCO : socyanate CN
–
: Cyanide
–
NC : Isocyanide

Neutral ligands : Carry no charge

e.g. NH3 (Ammine), H2O(Aqua), CO (Carbonyl), NO(Nitrosyl), O2(Dioxygen), N2(Dinitrogen),

PH3(Phosphene), PMe3(Trimethyl phosphene), PPh3(Triphenyl phosphene), N2H4(Hydrazine),
MeNH2(Methyl amine), EtNH2(Ethyl amine), R2O(Normal ether), R2S (Thio ether),

,
N
(Pyridine) (Benzene)

Positive ligands : Carry positive charge

e.g.
+
N2H5 : Hydrazinium. n n
+
NO : Nitrosylium or Nitrosonium
NO

2.5 NO B 0 3.0
NO B0
morestable
 Denticity : Denticity of a ligand represents number of co-ordinate bonds that it can form simultaneously to
same central metal atom/ion.

Monodentate ligands :
– – 3–
H : Hydride CH3O : Methoxide N : Nitride
F
–
: Flouride Me2O : Dimethyl ether NH3 : Ammine
– –
Cl : Chloride Me2S : Dimethyl thioether NH2 : Amide
– – 2–
Br : Bromide OCN : Cyanate NH : mide
I– : Iodide –
NCO : socyanate H2N – NH2 : Hydrazine
2– – –
O : Oxide SCN : Thiocyanate NO2 : Nitrite-N
2– – –
O2 : Peroxide NCS :  sothiocyanate ONO : Nitrite-O
– 2– –
O2 : Superoxide SO4 : Sulphate NO3 : Nitrate
2–
OH
–
: Hydroxide S O3 : Sulphite C5H5N : Pyridine
2– –
CH3COO : Acetate
(II) On the Basis of Denticity

O2 : Dioxygen S2O3 : Thiosulphate

2–
H2O : Aqua N3 :
–
Azide CO3 : Carbonate
CO : Carbonyl NO : Nitrosyl SnCl3
–
: Trichlorostannite
–
CN : Cyanide
–
NC : Isocynide
(Underlined Atoms are donar site of ligands.)
2– –
Among these monodentate ligands, some ligands like SO3 , SO4 , S2O3 , NO2 , NO3 , CH3 COO , CO3
2– 2– – – 2–

can also act as bidentate ligands, therefore these ligands are also called flexidentate ligands because
of their variable denticity. Such monodentate ligands form unstable four membered ring when they act as
bidentate ligands however their preferred denticity is one.

O 2– CH3 O 2– 2–
O
C C S S
– N+ N
O O O O – –
O O O (–)
O O O O O
O O
M M
M M M M
Carbonate Acetate Nitrate Nitrite Sulphate Sulphite

–
Polydentate ligands : Such ligands are capable of donating two or more lone pair e s to same central
metal atom/ion through co-ordinate bonds. While doing so they form 5/6 membered stable ring. Hence
such ligands are also called chelating ligands.

Bidentate Ligands : Having two donor atoms/coordination sites.

H2
– N
O O o M
C H2C
N N
M
H2C
M
N N
4
E
C
–
O O N M
Oxalate (ox) H2 Dipyridine (dipy) Phenanthrolene (phen)
(Symmetrical ligand) Ethylenediamine (en) (symmetrical ligand) (Symmetrical ligand)
(symmetrical ligand)

I H2C
H2
N
Me

HC
C rO
M
O
Ph

HC
C O
M

06
M –
C – C O
C O
– Me Me
O O
Glycinate (gly) Acetylacetonate (acac) Benzoylacetonate (bcac)
(unsymmetrical ligand) (symmetrical ligand) (unsymmetrical ligand)

E a
swine TEETH
me
after
 PMe2 dimethylphosphino
1 H2C H3C CH3
M * * H2C — CH — CH3
CH — CH
H2C | | | |
H2N NH2 H2N NH2
2 PMe2
M M
1, 2 bis (dimethylphosphino) Propylenediamine(pn)
Butylenediamine(bn)
ethane. (dmpe) (unsymmetrical ligand)
(symmetrical ligand)
(symmetrical ligand)
2NH4OH (Basic Mdm.)
NiCl2 + 2DMG –2H2O
[Ni(DMG)2]
(Rosy Red ppt.)
–
O–H---O In DMG donor sites are both
H3C — C N N-atoms rather than one O
2+ N = C — CH3
Ni and one N-atom because
H3C — C N in this case formed complex
– N = C — CH3 get extra stability due to
O - - H–O formation of additional
bis (dimethylglyoximato)nickel(II) stable rings through H-bonds.
Number of formed rings = 4
2 rings : 5 membered
2 rings : 6 membered
• Symmetrical ligands : Ligands having plane of symmetry (P.O.S.) w.r.t. donor sites and passing through
central metal atom/ion are called symmetrical ligands. e.g. ox , en , dipy , phen , acac.

• Unsymmetrical ligands : Ligands having no plane of symmetry (P.O.S.) w.r.t. donor sites and passing through
central metal atom/ion are called unsymmetrical ligands. e.g. DMG , gly , bcac , pn.
Note : No. of stable rings formed by a polydentate ligand = (denticity) – 1
Types of Polydentate Ligands

(i) Tridentate Ligand : Having three donor atoms/coordination sites.

H CH2 — CH2

H2C
N
M
5 NH2 prime
H2C
5 M
o
N
H2
Diethylenetriamine (dien) ethylene
(ii) Tetradentate Ligands : Having four donor atoms/coordination sites. diamine
H CH2 — CH2
N H
N
H2C CH2
M
H2C
CH2
N N
H2 H2
Triethylenetetraamine (trien)
(iii) Pentadentate ligand :
H H H
H2N – CH2CH2 – N – CH2CH2 – N – CH2 CH2 – N – CH2 CH2 – NH2
5 5 5 5
M
tetraethylenepentaamine (teten)
 (iv) Hexadentate Ligand :
CH2COOH
N
–
H2C CH2COOH OH 4–
H4 EDTA EDTA
H+
H2C CH2COOH (water insoluble) (water soluble)
N Ethylenediaminetetraacetic acid Ethylenediaminetetraacetate
CH2COOH
(H4EDTA)
Flexidentate character of EDTA4– at different pH value

Ligands Denticity
H4EDTA
–
lowly 2
H3EDTA [ethylenediamineacetate] 3 As pH of solution decreases
2– 4–
H2EDTA [ethylenediaminediacetate] 4 denticity of EDTA also decreases
3–
HEDTA [ethylenediaminetriacetate] 5
4–
EDTA [ethylenediaminetetraacetate] 6
* EDTA4– always gives octahedron geometry due to six coordinaion sites.

O O
– 2–
O
– 2–
C
CH2 O
CH2 C
–
No. of N – Ca – N Bond angles = 1 N O –
H2C N O
+2
No. of O – Ca – O Bond angles = 6 Ca
OR Ca
+2
H2C –
No. of N – Ca – O Bond angles = 8 N O –
N O
CH2 C
CH2
O
–
C—O –
O
O
2–
[Ca(EDTA)]
2– [Ca(EDTA)]

Ambidentate Ligands :When negative ligands have at least two different donor sites, but at a time of coordination
one donor site is used are called ambidentate ligands with monodentate behaviour. However Ambidentate
ligands having sp2 or sp3 hybridized central atom, can also act as flexidentate ligands.
–
M  SCN : Thiocyanate - S
–
M NCS : Thiocyanate - N
–
M OCN : Cyanate These ambidentate Ligands
–
M NCO : Isocyanate show monodentate behaviour.
–
M CN : Cyanide
–
M NC : Isocyanide
–
M  NO2 : Nitrite - N
–
M ONO : Nitrite - O
2–
M S2O3 : Thiosulphate -S
2–
M OS2O2 : Thiosulphate - O
2–
M SO3 : Sulphite - S These ambidentate Ligands can also show
M OSO2
2–
: Sulphite - O flexidentate behaviour as they are Non-linear.
–
M NOS : Thionitrite - N
–
M ONS : Thionitrite - O
–
M SNO : Thionitrite - S
 OH Mc N
434 0
MY N

med ri
my
meet
Dimethylyoal dimethylglyoxim CPM

unsymm.ligan tEHdenedia minetetra

acetiau .net night

EDtn

Inuit_one coin any coof

The co
any one cook

HEDTA Ln j cnz ou

Chi coot

Dente 61

into
EIF I mar
1 donor site
400 y o atoms
donor site
 PMe2 dimethylphosphine
I H2C H3C CH3
M * * H2C — CH — CH3
CH — CH
H2C | | | |
H2N NH2 H2N NH2
2 PMe2
M M
1, 2 bis (dimethylphosphino) Propylenediamine(pn)
Butylenediamine(bn)
ethane. (dmpe) (unsymmetrical ligand)
(symmetrical ligand)
(symmetrical ligand)
2NH4OH (Basic Mdm.)
NiCl2 + 2DMG –2H2O
[Ni(DMG)2]
(Rosy Red ppt.)
–
O–H---O In DMG donor sites are both
H3C — C N N-atoms rather than one O
2+ N = C — CH3
Ni and one N-atom because
5 5 in this case formed complex
H3C — C N
– N = C — CH3 get extra stability due to
O - - H–O formation of additional
bis (dimethylglyoximato)nickel(II) stable rings through H-bonds.
Number of formed rings = 4
2 rings : 5 membered
2 rings : 6 membered
• Symmetrical ligands : Ligands having plane of symmetry (P.O.S.) w.r.t. donor sites and passing through
central metal atom/ion are called symmetrical ligands. e.g. ox , en , dipy , phen , acac.

• Unsymmetrical ligands : Ligands having no plane of symmetry (P.O.S.) w.r.t. donor sites and passing through
central metal atom/ion are called unsymmetrical ligands. e.g. DMG , gly , bcac , pn.
Note : No. of stable rings formed by a polydentate ligand = (denticity) – 1
Types of Polydentate Ligands

(i) Tridentate Ligand : Having three donor atoms/coordination sites.

H CH2 — CH2

Denticity
stablerings
3
2 H2C
N
M
5 NH2 prime
H2C
o
N
H2
Diethylenetriamine (dien) ethylene
(ii) Tetradentate Ligands : Having four donor atoms/coordination sites. diamine
H CH2 — CH2
Denticity 4 N H
N
H2C
5
3 CH2
stable rings
M
H2C
CH2
N N
H2 H2
Triethylenetetraamine (trien)
(iii) Pentadentate ligand :
5 H H H
Denticity H2N – CH2CH2 – N – CH2CH2 – N – CH2 CH2 – N – CH2 CH2 – NH2
5 5 5 5
M
missing tetraethylenepentaamine (teten)
 (iv) Hexadentate Ligand :
CH2COOH
N
–
H2C CH2COOH OH 4–
H4 EDTA EDTA
H+
H2C CH2COOH (water insoluble) (water soluble)
N Ethylenediaminetetraacetic acid Ethylenediaminetetraacetate
CH2COOH
(H4EDTA)
Flexidentate character of EDTA4– at different pH value

Ligands Denticity
H4EDTA
–
lowly 2
H3EDTA [ethylenediamineacetate] 3 As pH of solution decreases
2– 4–
H2EDTA [ethylenediaminediacetate] 4 denticity of EDTA also decreases
3–
HEDTA [ethylenediaminetriacetate] 5
4–
EDTA [ethylenediaminetetraacetate] 6
V
* EDTA4– always gives octahedron geometry due to six coordinaion sites.

t O O
– 2–
6 2–
cDenticity
–
C O
CH2 O
CH2 C
–
No. of N – Ca – N Bond angles = 1 N O –
H2C N O
+2
No. of O – Ca – O Bond angles = 6 Ca
OR Ca
+2
H2C –
No. of N – Ca – O Bond angles = 8 N O –
N O
CH2 C
CH2
O
–
C—O –
O
O
2–
[Ca(EDTA)]
2– [Ca(EDTA)]

Ambidentate Ligands :When negative ligands have at least two different donor sites, but at a time of coordination
one donor site is used are called ambidentate ligands with monodentate behaviour. However Ambidentate
ligands having sp2 or sp3 hybridized central atom, can also act as flexidentate ligands.
–
M  SCN : Thiocyanate - S
–
M NCS : Thiocyanate - N
–
M OCN : Cyanate

ii
These ambidentate Ligands
–
M NCO : Isocyanate show monodentate behaviour.
M CN
M NC
–

–
:
:
Cyanide
Isocyanide
ident
M  NO2
–

–
: Nitrite - N
Denticity
I so
M ONO
M S2O3
2–
: Nitrite - O
: Thiosulphate -S
flexidented
2–
M OS2O2 : Thiosulphate - O
2–
M SO3 : Sulphite - S These ambidentate Ligands can also show
M OSO2
2–
: Sulphite - O flexidentate behaviour as they are Non-linear.
–
M NOS : Thionitrite - N
Ninitin
–
M ONS : Thionitrite - O
3
M SNO
–
: Thionitrite - S
mtn may
unstable
(III) Classical (Normal) and Nonclassical (-Acid) ligands.

Ligands
fi TI 0 0

 /
É Eptor
Classical Ligands (M
(Normal ligands)
L) Non classical Ligands (M
 L) a acid
When ligands can only donate their electron ( - acid /  - acceptor ligand) ligand
pair to the vacant orbital of the central metal
When ligands donate their electron
atom/ion through coordinate bond are called
classical (normal) ligands. pair to the vacant orbital of central metal atom/ion
– – – 2– – – and simultaneously accept electron pair from filled
eg. H , OH , NH3, H2O, NH2 , NH , F , CH3 ,
– d-atomic orbital of central metal atom/ion through
C2H5 , MeNH2
back bond either into vacant atomic orbital of
Types of Complexes : donor atom or into * MO of ligand are called
On the basis of M – L interaction non-classical (-acid) ligands.
complex compounds are of three types
(i) -Bonded complex compound :

(Having M L interaction)
donation 
3–

+
eg. [FeF6] , [Ag(NH3 )2] , [Fe(H2O)6]
3+
M L M L
 
R – Mg – X, Zn(C2H5)2, Pb(C2H5)4(TEL) Ligands of such Ligands of such
category are :
done
category are :
-Bonded OMC +
CO, NO, NO , N2, 2 - CH2 = CH2 (-ethene)

i
(ii) and -bonded complex compound PPh3, PF3, CN
– 6 - C6 H6 (-benzene)
–
-allyl, -cyclopentadienyl 5 - C5H5 (-cyclopentadienyl)
r
(Having M 
-donation
 L interaction)
–
3 - CH2 = CH – CH2 (-allyl)

CEO
-acceprance

8 EN
my
r donor
4 - CH2 = CH – CH = CH2 (-butadiene)

eg. M(CO)x
OMC
, [Fe(CN)
4–
] , [Ag(CN) ]
6 2
–
acceptor a dafftor
Organometallic Compound : OMC are type of complex
(iii) -bond complex compound compunds with metal carbon linkage (M  C linkage)

-donation where M : mostly metal / may be non-metal

(Having M 
L interaction) or metalloid with less EN value than carbon and
-acceprance C atom is of alkyl/aryl group including CO
5
eg. Cr(C6H6)2 , Fe( -C5H5)2 , K[PtCl3( – C2H4)]
2 NOTE : All OMC are complex compound but all
(ferrocene) (Ziese's salt) complex compounds are not OMC.

-Bonded OMC

IF
at 5 if
Co-ordination number (C.N.) of metal cation :
If'm C N second
Total number of e– pairs accepted by central metal atom /ion from donor atom of surrounding ligands is called
b
C.N. of central metal atom/ion. It is also called secondary valency of central metal atom / ion.

Table for Coordination Number of metal cation in a particular oxidn state (Stable oxidn state)
Monovlnt C.N. Divalent C.N. Trivalent C.N. Tetravalent C.N. Other C.N.
Cation Cation Cation Cation Cation
Cu+ 2, 4 Ti2+ 4, 6 Sc3+ 6 Ni4+ 6 Cr6+ 6
Ag+ 2, 4 V2+ 4, 6 Ti3+ 6 Pd4+ 6 Os8+ 6
Au+ 2, 4 Cr2+ 4, 6 V3+ 6 Pt4+ 6 Os6+ 6
Mn2+ 4, 5, 6 Cr3+ 6 Pb4+ 6
Fe2+ 4, 5, 6 Mn3+ 6 Sn4+ 6
Co2+ 4, 6 Fe3+ 6 Mo4+ 6
Ni2+ 4, 5, 6 Co3+ 6
Cu2+ 4, 5, 6(rare) Rh3+ 6
Zn2+ 4(Alys Td),6(H2O) Ir3+ 6
Cd2+ 4, 6 Ru3+ 6
Hg2+ 2, 4 Os3+ 6
Pd2+ 4(Alwys Sq.pl.) Ag3+ 4(Alwys Sq.pl.)

Pt2+ 4(Alwys Sq.pl.) Au3+ 4(Alwys Sq.pl.)

Pb2+ 4, 6 Al3+ 4, 6
Sn2+ 4, 6 Bi3+ 4, 6
Ca2+ 4, 6
Mg2+ 4, 6
Be2+ 4(Alwys Td)

IMPORTANT POINTS
1. NH4+ cation never act as ligand.
2. Metal cation with >+2 (more than +2) oxidation state usually have their stable C.N. = 6 with any ligands.
3. Monodentate ligands having more than one lone pair on donor site can act as bridging ligands except
CO (act as bridge ligand with equal sharing of electron of carbon).

X
– Bridging ligand
idii imine
M M
4. Neutral ligands in which two different atoms are having lone pairs, then preferential donor site is less
electronegative atom eg. CO, NO.
5. N2H4 never act as bidentate ligand because it will form unstable three membered ring with central metal

atom/ion eg. H2N NH2

M
6. Ligands containing carbon and nitrogen atom as donor sites are called strong field ligands (SFL) and rest of
them are considered as weak field ligands (WFL) in spectrochemical series. (Except N3– ion is WFL)
7. Cr3+  Coordination Number (C.N.) = 6
3
weakfield
[Cr(NH3)5(SO4)]+ : SO42– act as monodentate ligand.
+ 2–
[Cr(NH3)4(SO4)] : SO4 act as bidentate ligand.
ligand
 QUESTIONS FOR PRACTICE–1

Single Choice Questions :

1. Consider the complex [Co(NH3)4CO3]ClO4 , in which coordination number, oxidation number and number of
d-electrons on the metal are respectively
(A) 6, 3, 6 (B) 6, 2, 7 (C) 5, 3, 6 (D) 5, 3, 7

2.
–
The comon features among the species CN , CO and NO+ are Chaining
(A) Bond order three (B) Isoelectronic M Ligand
(C) All are -donor and -acceptor (D) All of these

3. The -acid ligand which uses its d-orbital during synergic bonding in its complex compound.

(A) CN– (B) PR3 (C) NO (D) N2

4. Statement-1 : In N2H4, any one N-atom can coordinate with central Metal cation in a coordination compound.
Statement-2 : N2H4 can also act as ambidentate ligand.
(A) Statement-1 is true, Statement-2 is true and Statement-2 is correct explanation for Statement-1
(B) Statement-1 is true, Statement-2 is true and Statement-2 is NOTcorrect explanation for Statement-1
(C) Statement-1 is true, Statement-2 is false
(D) Statement-1 is false, Statement-2 is true

Single Choice Questions :

5. Which of the following does not act as -acid ligand.

(A) F– (B) O22– (C) N2H4 (D) C2H2

6. Which of the following ligand(s) can act as -acid ligand.

(A) -cyclopentadienyl (B) -Allyl (C) B3N3H6 (D) -cyclopentadienyl

Subjective :

7. Calculate value of “x  y” if x is the total number of  bonds and y is total number of  bonds in both ligands
EDTA and Phenanthrolene respectively.
{EDTA = Ethylene diamine tetraacetate, Phen = 1, 10 – N, N-Phenanthrolene}

8. Consider the following ligands NH2–, acac, OH–, Gly, O2–, Phen, DMG, NO2–, CO32–, Cl–, CH3COO–, en, SO42–.
Then calculate value of "P + Q – R – S"
Here P : Total number of ligands which act as bridging as well as monodentate only.
Q : Total number of flexidentate ligands
R : Total number of symmtrical bidentate ligands
S : Total number of unsymmtrical bidentate ligands

9. Find the number of ligand(s) which is/are classical ligand(s).

CO, NO, C2H4, 3-C3H5–, H–, PH3, N2H4, C5H5–, C6H6

10. Find the number of ligands which may act as  donor as well as  acceptor non-classical ligand.
CO, PH3, PF3, C3H5–, C5H5–, NO, C6H6, CN–.
 ANSWER KEY
PRACTICE–1

1. A 2. D 3. B 4. C 5. ABC 6. ABCD 7. 5
8. 3 9. 2 10. 3
 INORGANIC CHEMISTRY

NOTES

COORDINATION
COMPOUNDS co
Biz
PART 2 13 0730

metal FE
and
Synergic
Bonding
TL
YCCOCB.OC3
innate
 Synergic bonding in metal carbonyl complexes : M(CO)x

-back donation BE CO
(back bond)
fixed'd B o of
* m.o
co 3 0

If
Weak 
is 
–ve, +ve or
M
donation
: C  O
Empty 
zero charge
co cot
zero NBMO with
slight AB 3.0 73.0
7
(M L) B.O. > 1
character
CO Bond order < 3 e removed
Synergic bond in metal carbonyl complexes
tromani's
Effects of synergic bonding :
In metal carbonyl complexes during synergic bonding metal-ligand bond gets stronger and its bond order
int

increases (M  L B.O. > 1). While within CO ligand carbon-oxygen bond order decreases (CO B.O. < 3)
because already existing -bond gets weaker.

CO bond order CO bond length

(1) Free CO molecule = 3.0 = 1.128 Å
(2) M(CO)x < 3.0 > 1.128 Å
(3) H3B  CO > 3.0 < 1.128 Å MIT
Specific colour of all carbonyl complexes is due to metal to ligand (M  L) charge transfer
phenomenon which occurs through synergic bond.

Synergic bond in Zeise’s salt K[PtCl3(–C2H4)].H2O : K EE no sinus

Zeise’s salt is yellow coloured due to charge transfer phenomena. It contains one H2O molecule as water of
crystallization.

Many I 42.0
IEEE.glqG.oofIC
-back acceptance
(back bond)

B M C I A
CH2
ethylene
Cl a 
CH2
2+
1M
Pt
  CH2  r
K+ 2+
Pt  donation aliens
 a (not counted)
Cl b  CH2
Cl
(Trans Effect in
trans sq.pl. geometry)
(M L) B.O. > 1
CN 4 I (C = C) B.O. < 2

in
B L of Cm
IFI
In Zeise’s Salt : K[PtCl3(2 - C2H4)] one
Equivalent (Pt – Cl) Bond Length = 2
Total number of -bonds = 8 normal Can cm
Total number of -bonds = 2 (-donation is not counted as it is only shifting of
1 34A
 e– density of ligand towards CMA/ion).
271.34A
PILS
Experimental evidence of synergic bonding in metal carbonyl complexexs by IR spectroscopy.

-back bond

Weak  
–ve, +ve or 
Zero charge M donation C  O

CO Bond order < 3

(M L) B.O. > 1

B 0 of cut due to
 CO (wave no.) 
1 k
2c 
cm –1 Back Bonding
as the Back Bonding B o of co
where
CO : Stretching frequency (wave no.) of CO ligand (energy required to stretch CO bond).
c : Velocity of light.
8 8
Me M
CIII
k : Force constant of CO ligand.
 : Reduced mass of CO ligand.

ICE
Strength of back bond  –ve charge on metal atom
1 1
Strength of back bond    CO bond length.
CO CO bond strength (Bond Energy) α
or Bond order 1
Strength of back bond  (M  L) bond strength/energy 
M  L Bond length

QUESTIONS FOR PRACTICE–2

Single Choice Questions : BackBonding α co α B 0 of co α
1. In which of the following carbonyl complexes, CO stretching frequency is minimum?
(A) [Cr0(CO)6] (B) [Fe+22(CO)6]2+ i(C) [V t (CO)6]
–1 –
(D) [Mnt
+(CO) ]+
J 6

2. In isolated state, CO bond length is 1.128 Å. Comment on CO bond length in metal carbonyl complexes.
(A) 1.128 Å (B) 1.115 Å (C) 1.151 Å (D) 1.751 Å
5 2
3. In which of the following carbonyl complexes, CO bond strength is maximum. B o of 6
(A) [Fe0(CO)5] (B) [Mn+1(CO)6]+ (C) [V–(CO)6]– (D) [Cr0(CO)6]0
in MCO 30

4. In NO complexes , M  NO back bonding the d-orbital(s) of the metal which participate in bonding with
*-Molecular orbital of NO ligand will be :
(A) d (B) dxz , dyz (C) only dxz (D) dxy , d
x2 y2 z2

5. Which of the following complex is having largest C – O bond length

(A) [V(CO)6]¯ (B) [Mn(CO)6]+ (C) [Mn(CO)5]¯ (D) [Ti(CO)]6]2–

6. The Infra-red stretching frequency ( CO ) of given compounds P to S follows the order

(P) Mn(CO)6 (Q) CO (R) H3B  CO (S) [V(CO)6]–

(A) P > R > S > Q (B) S > P > R > Q (C) Q > S > P > R (D) R > Q > P > S

PILS
7. Correctly matched CO (stretching frequencies of CO ligand in cm–1) with their respective complex species, is :

[Cr(CO)6] [Ti(CO)6]2– [Mn(CO)6]+

(A) 1859 2000 2143

(B) 2000 2100 1748

(C) 2184 2100 1748

(D) 2000 1748 2100

8. H.O.M.O. (Highest Occupied Molecular Orbital) of CO molecule is
(A) Non-bonding M.O. with slight antibonding character
(B) Non-bonding M.O. with slight bonding character
(C) Pure non-bonding M.O.
(D) None of these

9. Statement-1 : In Zeise's salt C – C bond order regarding ethylene molecule is less than two.
Statement-2 : Ethylene accepts electron pair from filled d-orbital of Pt2+ into its vacant bonding
M.O.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.

One or more than one correct :

10. For the metal-olefin complex (i) [PtCl3(C2H4)]– and (ii) [PtCl3(C2F4)]–, the correct statement is/are
(A) carbon-carbon bond length is same both in (i) and (ii)
(B) carbon-carbon bond length in (i) is smaller compared to that of (ii)
(C) carbon-carbon bond length in (i) is larger compared to that of (ii)
(D) Both complexes are diamagnetic

Comprehension-1 (11 to 15) :

Two important physical evidences supporting the synergic bonding in non-classical complexes are bond
lengths and vibrational spectra. Vibrational spectra is based on the fact that the compression and extension
of a bond may be likened to the behaviour of a spring and obeys Hook's law

1 k
 = cm–1
2c 

where , k = force constant of the bond which is directly proportional to bond strength.
 = Reduced mass of ligand.

 = stretching frequency of the bond

c = velocity of light

11. The carbonyl compound that has least value of  for CO is :

(A) [Mn(CO)6]+ (B) [Mn (dien) (CO)3]+ (C) [Cr(CO)6] (D) [Cr(dien) (CO)3]

12. In which complex, M – C bond order is maximum :

(A) [Fe (CO)4]2– (B) [Co(CO)4 ] – (C) H[Co(CO)4] (D) [Ni(CO)4]

PILS
13. Which of the following orbital of ligand can participate in back bonding in non-classical complexes.

(A) M.O. (B) All d-orbitals (C) * M.O. (D) All

14. In which of the following complex stretching frequency for CO ligand is least as well as bond energy of
M – C bond is higher.

(A) (dien) Mo(CO)3 (B) (Et3P)3 Mo(CO)3 (C) (F3P)3 Mo(CO)3 (D) (Cl3P)3 Mo(CO)3

15. In which of the following ligand, bond order does not change during synergic bonding in their respective
complexes

(A) CO (B) N2 (C) CH2 = CH2 (D) PEt3

Comprehension-2 (16 to 17)

If in the mixed carbonyl, the other ligand is also pi acceptor, it would compete with the ligang CO for gaining
of d electron density. Higher will be the extent of back donation in CO, leaser will be the stretching vibration
frequency for C—O bond.

16. Select the correct order of M—C bond order in the following molecule and ions :
(A) [Ni(CO)4] > [Co(CO)4]– > [Fe(CO)4]2– (B) [Ni(CO)4] = [Co(CO)4]– = [Fe(CO)4]2–
(C) [Co(CO)4]– > [Fe(CO)4]2– > [Ni(CO)4] (D) [Ni(CO)4] < [Co(CO)4]– < [Fe(CO)4]2–

17. Select the correct order of C—O bond length in the following molecules
(A) [Mo(CO)3 (PF3)3] > [Mo(CO)3 (PCl3)3] > [Mo(CO)3 (P(Me)3)3]
(B) [Mo(CO)3 (P(Me)3)3] > [Mo(CO)3 (PF3)3] > [Mo(CO)3 (PCl3)3]
(C) [Mo(CO)3 (PCl)3)3] > [Mo(CO)3 (P(Me)3)3] > [Mo(CO)3 (PF3)3]
(D) [Mo(CO)3 (PF3)3] < [Mo(CO)3 (PCl3)3] < [Mo(CO)3 (P(Me)3)3]

Comprehension-3 (18 to 19)


Crystallographic evidence for M – CO bonding model describes that greater the extent of M  CO back
bonding, more the C – O bond will be lengthened and M – C bond will be shortened. The  interaction, on the
other hand, will have opposite effect on the C – O bond length because the lone pair on carbon that is utilized
in forming  bond is in a slightly antibonding MO of the carbon monoxide.

18. Which of the following species are correctly matched regarding their CO (stretching frequencies of CO

ligand in cm–1)

 of CO  of CO+  of CO in [V(CO)6]–

(A) 2184 2143 1859

(B) 2143 1859 2184

(C) 1859 2000 2143

(D) 2143 2184 1859

19. For which metal ligand interaction bond order of ligand remains almost same :
(A) M – CN (B) M – CO (C) M – N2 (D) M – PF3

PILS
Effective atomic number (EAN) of central metal atom/ion : 2 26 26 é
Total number of electrons present on central metal atom (CMA) / ion after accepting electron pairs from
surrounding ligands is called EAN (effective atomic number) of central metal atom/ion.

EAN = Z — O.S. + 2 × C.N

Atomic Oxidation Coordination

number of state of number
CMA metal of
atom/ion CMA/ion

Sidwick’s Rule of EAN :

According to this rule, when EAN of central metal atom or ion in complex compound is equal to nearest
noble gas configuration, then stability of such complex is more.

Complex compound EAN

K4[Fe+2(CN)6]–4 26 – 2 + 6 × 2 = 36
[Cr0(CO)6] 24 – 0 + 6 × 2 = 36
[Fe0(CO)5] 26 – 0 + 5 × 2 = 36 EAN is equal to nearest noble gas configuration
[Co3+ (EDTA)]– 27 – 3 + 2 × 6 = 36 following sidwicks rule of EAN
[Co+3(en)3]+3 27 – 3 + 2 × 6 = 36

Complex
K3[Fe3+(CN)6]
[Ni+2(DMG)2]
EAN
26 – 3 + 12 = 35
28 – 2 + 2 × 4 = 34
E
(Rosy red ppt)
[Fe3+(H2O)6]+3 26 – 3 + 12 = 35 Not following sidwicks rule of EAN
K[Pt+2Cl3( – C2H4)]0 78 – 2 + 4 × 2 = 84
(Ziese salt)
V(CO)5 23 – 0 + 5 × 2 = 33

Violation of sidwick’s rule of EAN :

Stability order : K3 [Fe+3(CN)6] > K4[Fe2+(CN)6]

EAN = 35 EAN = 36
ExceptionofEAnne
In metal carbonyl complexes, when EAN of CMA/ion is either less or more than nearest noble gas
configuration, then they have tendency to achieve nearest noble gas configuration. In this way, such carbonyl
complexes act as oxidant and reductant respectively.
–e
[Mn0(CO)6] (less stable) oxidation [Mn+1(CO)6]+ (stable)

EAN = 25 – 0 + 12 = 37 (Acts as Red. Agt.) EAN = 25 – 1 + 6 × 2 = 36

+e
[V0(CO)6]0 (less stable) reduction [V–1(CO)6]– (stable)

EAN = 23 – 0 + 12 = 35 (Acts as Oxd. Agt.) i EAN = 23 + 1 + 6 × 2 = 36

Note : In carbonyl complexes, metal may have –ve O.S. (–2, –1) because of stabilisation due to synergic bonding.

+ 2e–
[Fe0(CO)4]0 (less stable) [Fe–2(CO)6]– (stable)
reduction
EAN = 26 – 0 + 8 = 34 (Acts as Oxd. Agt.) EAN = 26 + 2 + 8 = 36

PILS
 Sandwich compounds :

   
0
Cr Fe2+
   

Cr(6 – C6H6) Fe+2(5 – C5H5)2 (Ferrocene)

EAN = 24 – 0 + 2 × 6 = 36 EAN = 26 – 2 + 2 × 6 = 36
Note : If more than one -electron pairs are involved in coordination in -complexes with central metal
atom/ion then its coordination number is not defined.

–e +

ini
NO (B.O. = 2.5) NO (B.O. = 3)
just Neutral ligand
3e -donor
–
Positive ligand
2e -donor
– 0.5
M M
8N 2.52
2.0

Conversion of CO metal carbonyl into metal nitrosyl complexes. (When CO lgds are replaced by NO lgds)

Cr(CO)6 +2NO Cr(CO)3(NO)2 +2NO Cr(NO)4

Ex. –3CO –3CO
(carbonyl complex) (nitrosyl complex)
EAN=24–0+6×2=36 EAN=24–0+3×2+2×3=36 EAN=24–0+3×2+2×3=36

Fe(CO)5 +2 NO
–3CO
Fe(CO)2(NO)2 2110 can be replaced
EAN=24–0+5×2=36 EAN=26–0+3×2+2×2=36
by 3 co

* Calculation of EAN of central metal atom in polynuclear carbonyl complexes.

All polynuclear carbonyl complexes have -bonds between metal atoms.
(CO)5Mn -bond Mn(CO)5
Ex. Mn2(CO)10 or
Is 1mn67s
CO CO CO CO Miklos 350
0 0 25 10
CO Mn
-bond
Mn CO EAN

CO CO CO CO

2  25  2  10  2  1 (  bond)
EAN of Mn atom = = 36
2

Mn2(CO)10 (stable) In absence of reductant ; [Mn(CO)5] (less stable) + electron

–
[Mn(CO)5] (stable)
EAN=36 dimerisation occurs through EAN=35 Redox reaction EAN=36
formation of -bond act as oxidant
in presence of inpresence
reductant
of seductant
PILS
Ex. Fe2(CO)9 or (CO)3Fe(CO)3Fe(CO)3
Co act as bridgingligand
O
5.0 2 also
OC C CO

0 -bond 0

timing OC Fe Fe CO
terminal
OC C CO
O

C
103Fe a Fe401
O

EAN of Fe atom = E
26  2  6  2  3  2  1 2
2
= 36

CO B.O. (terminal) > CO B.O. (bridging), hence CO (terminal) > CO (bridging)

Co2(CO)8 (stable) In absence of reductant ; [Co(CO)4] (less stable) + electron [Co(CO)4]– (stable)
Ex.
EAN=36 dimerisation occurs through EAN=35 Redox reaction EAN=36
formation of -bond act as oxidant
in presence of
reductant
cocco
Co2(CO)8 exists in two formes as follows

Co2(CO)8 (Non-bridge form) (CO)3Co(CO)2Co(CO)3 (Bridge form) 27 8 350

CO CO O
CO CO
CO C CO
0 -bond 0 0 0
Co Co CO Co -bond Co CO

CO CO CO C CO 217981dL
CO CO O
Non-bridge form exists in liquid state Bridge form exists in solid state

CO B.O. (terminal) > CO B.O. (bridging), hence CO (terminal) > CO (bridging)

QUESTIONS FOR PRACTICE–3

Single Choice Questions :
1. The effective atomic number of Co(CO)4 is 35. It attain stability by
(A) Oxidation of [Co(CO)4] (B) Reduction of [Co(CO)4]
(C) Dimerisation of [Co(CO)4] (D) By both (B) and (C)

2. If CO ligands are substituted by NO in respective neutral carbonyl compounds then which of the following will
not be correct formula
(A) Fe(CO)3(NO)2 (B) [Cr(–C6H6) (NO)2] (C) Ni(CO)(NO)2 (D) Cr(NO)4

3. EAN of the elements (*) are equal in:

* * * *
(A) N i (CO)4, [ Fe (CN)6]4– (B) [ N i (en)2]2+, [ Fe (H2O)6]2+
* * * *
(C) [ Co (CN)6]3–, [ Fe (CN)6]3– (D) [ N i (en)2]2+, [ Sc (H2O)6]3+
4. Which of the following is an oxidizing agent?
(A) Mn(CO)5 (B) Fe(CO)5 (C) Mn2(CO)10 (D) Fe2(CO)9
PILS
5. Choose the correct option regarding the following complex compound which follows (F) and does not follow
(NF) the sidgwick EAN rule:
(I) [(Ph3P)2PdCl2PdCl2] (II) [NiBrCl(en)] (III) Na4[Fe(CN)5NOS] (IV) Cr(CO)3(NO)2
(I) (II) (III) (IV) (I) (II) (III) (IV)
(A) NF NF NF NF (B) F F NF F
(C) NF NF F F (D) NF NF F NF

6. Oxidation number of Cr in the following complex is

3+
O2
(H2O)4Cr Cr(H2O)4
O O

(A) 3 (B) 6 (C) 4 (D) 5

7. In carbonyl complex [Fe(CO)4]2–, if maximum number of CO ligands are substituted by NO, then its correct
formula is
(A) [Fe(CO)(NO)2]2– (B) [Fe(NO)3]2– (C) [Fe(NO)3] (D) [Fe(CO)(NO)2]–

Comprehension (8 to 10)
Sidwick EAN rule says that metal carbonyl complex compound has the tendency to achieve the EAN of 36,
54 and 86 for First, Second and Third transition series elements.

8. Which of the following complex acts as reducing agent based on Sidwick EAN rule.
(A) Mn(CO)5 (B) Mn2(CO)10 (C) Mn(CO)6 (D) [V(CO)6]¯

9. Which of the following complex is following sidwick EAN rule.

(A) [Ag(S2O3)2]3– (when only 'S' atom is the donor atom)
(B) [Cd(CN)4]2– (C) [Pt(en)2]2+ (D) [Mo(– C3H5) Br(NH3)2]°

10. Which of following statement is not correct regarding complex "Ferrocene".

(A) EAN of central atom in ferrocene is not equal to its nearest noble gas
(B) Molecule is having aromatic character
(C) It has sandwich like structure
(D) Two rings act as -donor ligand.
Match the column :
11. Column-I Column-II
(A) Mn(CO)5 (P) Oxidizing character
(B) Fe(CO)5 (Q) Reducing character
(C) Co(CO)4 (R) Synergic bonding
(D) Mn(CO)6 (S) Stabilized by dimerization
(T) Doesnot follow Sidgwick rule of E.A.N.
Subjective :
NO
12. M(CO) x (NO) y   M(NO)z
– CO

Where EAN of metal (M) in both product and reactant is same and it is 54. Then calculate value of (x + y – z).
(where x, y and z are natural numbers and M belong to 6th group according to long form of periodic table)

13. Consider the following carbonyl complex compounds.

(i) Mo(CO)x (ii) Hy [Cr (CO)5]
Then calculate value of |x – y|.

14. Consider the following two complex ions : (I) [Co(en)3]n+ (II) [Rh(EDTA)]m–
If both complex ions follow Sidwick's rule of EAN, then calculate the value of expression (n + m)2.
 PRACTICE–2

1. C 2. C 3. B 4. B 5. D 6. D 7. D
8. A 9. C 10. CD 11. D 12. A 13. A 14. A
15. D 16. D 17. D 18. D 19. D

PRACTICE–3

1. D 2. A 3. A 4. A 5. C 6. A 7. A
8. C 9. B 10. A 11. A  P, R, S, T ; B  R ; C  P, R, S, T ; D  Q, R, T ;
12. 1 13. 4 14. 16
INORGANIC CHEMISTRY

NOTES

COORDINATION
COMPOUNDS
PART 3
 RULES FOR IUPAC NAMING OF COMPLEX COMPOUNDS
1. In IUPAC naming of complex compound positive (cationic) part is named first, whether it is simple or complex
followed by naming of negative (anionic) part.
2. In IUPAC naming of complex ion, ligands are named first according to alphabetical order of their names
followed by naming of central metal atom / ion.
3. When there are several monodentate ligands of the same type, then prefix di, tri, tetra, penta, hexa etc. are
provided to the ligands. If monodentate ligand’s name already contain any of these prefix then to avoid
confusion, ‘bis’, ‘tris’, ‘tetrakis’ ‘pentakis’ are used instead of di, tri, tetra, penta etc. and ligand’s name is
placed in parenthesis. Bis, tris prefix is also provided to chelating ligands forming stable 5/6 membered ring
with central metal atom/ion and also with -acid ligands which can be involved in -donation with central
metal atom/ion.
4. Negative ligands have suffix — o,
Positive ligands have suffix — ium, Rio nitrosonium
Neutral ligands have no specific suffix.
Monodentate ligands : (with their IUPAC names)
– – 3–
H : Hydrido CH3O : Methoxo / Methoxido N : Nitrido
– –
F : Flouro/Flourido –
OCN : Cyanato NH2 : Amido
– – 2–
Cl : Chloro/Chlorido NCO : socyanato NH : mido
– – –
Br : Bromo/Bromido SCN : Thiocyanato/Thiocyanato - S NO2 : Nitro/Nitrito-N
–
I : Iodo/Iodido –
NCS : sothiocyanato/Thiocyanato-N ONO
–
: Nitrito/Nitrito-O
2– 2–
O : Oxo/Oxido SO4 : Sulphato NO3
–
: Nitrato
2–
O2 : Peroxo/peroxido 2–
SO3 : Sulphito CN
–
: Cyano / Cyanido
–
O2 : Superoxo/Superoxido S2O3 :
2–
Thiosulphato CH3COO
–
: Acetato
– – 2–
OH : Hydroxo/Hydroxido N3 : Azido C2O4 : Oxalato
2–
CO3 : Carbonato
Note : Underlined Atoms are donar site of ligands. –
2 SnCl3 : Trichlorostannito
But negative organic ligands having '–yl' suffix of hydrocarbon origin are not replaced by '-o'

CH3– – Methyl – – Cyclopentadienyl

C2H5– – Ethyl 71430

5. Usually common names are provided to the neutral ligands Ammanis
except NH3(Ammine), H2O(Aqua/Aquo), CO(Carbonyl), NO(Nitrosyl),
Ammine
eg. N2(Dinitrogen), O2(Dioxygen), PH3(Phosphene), PMe3(Trimethyl phosphene), PPh3(Triphenyl phosphene),
N2H4(Hydrazine), MeNH2(Methyl amine), EtNH2(Ethyl amine), Me2O(Dimethyl ether),
Me2S(Dimethyl thioether), C6H6(Benzene), C5H5N(Pyridine)

6. In IUPAC naming of complex anion, central metal atom has suffix ‘–ate’ along with its latin or english name
but in case of complex cation/complex neutral molecule central metal atom has no specific suffix with its
common english name.
Metal in complex anion –ium  + ate
Cr Chromate
Pd Palladate
Os Osmate
Ir Iridate
Usually latin names are used for those metals whose symbol is derived from corresponding latin names,
Cu(Cuprum); Fe(Ferrum); Ag(Argentum); Na(Natrium); Au(Aurum); K(Kalium); Sn(Stannum); Pb(Plumbum)
Except : Hg(Mercury); Sb(Antimony); W(Tungsten).

III
7. Oxidation state of central metal atom/ion is represented by roman numerals including zero immediate after
metal’s name in parenthesis.

8. In case of polynuclear/bridging complex compound,  - prefix is provided to bridging ligand when it is coordinated
with two metal atoms/ion. When bridinging ligand is coordinated with more than two metal atoms, then prefix
3, 4, .........etc. are provided to the bridging ligands.
IUPAC naming of complex compounds :
(1) 2
K4[Fe(CN)6]  Potassium hexacyanido ferrate(II)
(2) [Cu2+(NH3)4]2+ SO2–
4
(Switzer’s reagent)  Tetraamminecopper(II) sulphate
(3) K+[Ag+(CN)2]  Potassium dicyanidoargentate(I)
(4) K 31 [Cu+1(CN)4]–3  Potassium tetracyanidocuprate(I)
4  2 –1
(5) [Pt Cl2 (NH3 )4 ]2 [Pt Cl4 ]–2  Tetraaminedichloridoplatinum(IV) tetrachloridoplatinate(II).
3
(6) [Cr(acac)3–1 ]0  Tris(acetylacetonato)chromium(III)
2 –1
(7) [Ni(DMG)2 ]0  (Rosy red ppt)  Bis(dimethylglyoximato)nickel(II)
(8) [Co+3(EDTA)–4]–  Ethylenediaminetetraacetatocobaltate(III) ion
0
(9) Cr(CO)6  hexacarbonylchromium(0)
(10) Fe(CO)5  Pentacarbonyliron(0)
(11) Fe+2(5 – C5H5)2 (Ferrocene)  bis(5 – cyclopentadienyl)iron(II)
(12) Cr0(-C6H6)2  bis(6-benzene)chromium(0)
3 –1
(13) [Cr Cl2 (H2 O)4 ]Cl.2H2 O  tetraaquadichloridochromium(III) chloride-2-water.
or tetraaquadichloridochromium(III) chloride dihydrate.
3
(14) H+1 [AuCl4 ]–1 (complex acid)  tetrachloridoauric (III) acid
4
(15) H2 [Pt Cl6 ] (complex acid)  hexachloridoplatinic(IV) acid.
2 1
(16) Na22 [Fe(CN)5– (NO)] –2 (Sodium Nitroprusside)  Sodiumpentacyanidonitrosoniumferrate(II)
Note : Sodium Nitroprusside is used for specific test of S2– ion by following reaction.
2 –1 –1
Na2S + Na2[Fe2+(CN)5(NO)]  Na4 [Fe(CN)5 (NOS)] (Purple colour compound)
(Sodium Nitroprusside) Sodium pentacyanidothionitrito–N-ferrate(II)
1
1 2
(17) [Fe1
1
(H2O)5 (NO)]SO –2
4
(Brown ring complex)  Pentaaquanitrosyliumiron(I) sulphate
Note : NO is present as positive ligand in both sodium nitroprusside (expt = 0 B.M.) & Brown ring complex
(expt = 15 B.M.)

4 H ) (-C H ) ]
1 2 1 2
(18) [Ti(-C5 5 2 5 5 2  Bis(5-cyclopentadienyl)bis(cyclopentadienyl)titanium(IV)

donor
I a

meaning

 aeratosinold
És
Ti4+
 
Gae

Its 6
EÑ4 Mrs 0
2 cN
 4

As per old convention complex is written as

[M(–ve ligand) (neutral ligand) (+ve ligand)]n±

As per new convention ligands are written in alphabetical order

[M (ligands are arranged in alphabetical order)]n±
6 –1 –2 –1/0 / 2 0
(19) K 2 [Cr(CN)2 (O)2 ( O2 2)(NH3 )]2– (Old convention) Potassium amminedicyanidodioxidoperoxidochromate(VI)

3 –2 –1/ –2 0 0
(20) K 2 [Co(O)2 ( O2 )(NH3 )(O2 )2 ]2–(Oldconvention)Potassiumamminebis(dioxygen)dioxidosuperoxidocobaltate(III)

6
K 2 [Cr(NH3 )(CN)2 (O)2 (O 2 )]2– (New convention) Potassium amminedicyanidodioxidoperoxidochromate(VI)
21
3
K 2 [Co(NH3 )(O2 )2 (O)2 (O2 )]2 – (New convention)Potassiumamminebis(dioxygen)dioxidosuperoxidocobaltate(III)
122
IUPAC naming of bridging/polynuclear complex compounds :

4+
NH3 –1 NH3 NH3
NH3 O2

Cr+3 Cr+3
–1
NH3 NH2 NH3
NH3 NH3

(1) Tetraamminechromium(III)--amido--superoxidotetraamminechromium(III) ion.

(2) -amido--superoxido octaammine dichromium(III) ion.
(3) -amido--superoxido bis{tetraamminechromium(III)} ion.

4+
–1
OH
3+ 3+
(en)2 Co Co(en)2
–1
OH

(1) bis(ethylenediamine)cobalt(III)di--hydroxidobis(ethylenediamine)cobalt(III)ion.
(2) di--hydroxido tetrakis(ethylenediamine)dicobalt(III)ion
(3) di--hydroxido bis{bis(ethylenediamine)cobalt(III)}ion
(4) bis{-hydroxidobis(ethylenediamine)cobalt(III)}ion

+2 2– – 0 +2 2– – 0
[Be4 (O )(CH3COO )6] [Zn4 (O )(CH3COO )6]
+2 +2
Be Zn
Ac Ac Ac Ac
Ac +2 Ac +2
+2 Be O Be +2 Zn O Zn
Ac Ac
Ac Ac Ac Ac
+2 Be +2 Zn
(Common name : Basic Beryllium Acetate) (Common name : Basic Zinc Acetate)
IUPAC name : Hexa--acetato--oxido tetraberyllium(II) IUPAC name : Hexa--acetato--oxido tetrazinc(II)

Note : Adjacent donor site of chelating ligand always occupy adjacent position of geometry.
Text Example - 1 : I.U.P.A.C. name of the following complex Compounds :
1. K2[HgI4]  Potassium tetraiodidomercurate (II)
2. LiAlH4  Lithium tetrahydridoaluminate (III)
3. K3[Fe(CN)6]  Potassium hexacyanidoferrate (III)
4. K2[Pt Cl6]  Potassium hexachloridoplatinate (IV)
5. [PtCl2(NH3)2]  Diamminedichloridoplatinum (II)
6. [Co(NH3)6]Cl3  Hexaamminecobalt (III) chloride
7. [Fe(en)3]Cl3  Tris (ethylenediamine) iron (III) chloride
8. K3[Ir(C2O4)3]  Potassium trisoxalatoiridate (III)
9. [Co(NCS)(NH3)5]Cl2  Pentaammineisothiocyanato cobalt (III) chloride
Pentaamminethiocyanato–N–cobalt (III) chloride
10. [CoBr(ONO)(en)2]+1  Bromidobis(ethylenediamine) nitrito-O cobalt (III) ion
11. K2[Mo(CN)6]  Potassium hexacyanidomolybdate (IV)
12. [CoI(NH3)5]SO4  Pentaammineiodidocobalt (III) sulphate
13. [Co(NH3)6] [Co(ONO)6]  Hexaammine cobalt (III) hexanitrito–Ocobaltate (III)
14. (NH4)2[Pt(SCN)6]  Ammonium hexathiocyanato–S platinate (IV)
15. [Co(NO2)3(NH3)3]  Triamminetrinitrito-N-cobalt (III)
16. (NH4)3[Cr(NCS)6]  Ammonium hexaisothiocyanatochromate (III)
17. [Pt(NH3)4][PtCl4]  Tetraammine Platinum (II) tetrachloridoplatinate (II)
18. (NH4)4[Mo(CN)8]  Ammonium octacyanidomolybdate (IV)
19. [FeF6]3 –  Hexafluoridoferrate (III) ion
20. [CoCO3(NH3)5]Cl  Pentaamminecarbonatocobalt (III) chloride
21. K3[Fe(NH2)6]  Potassium hexaamidoferrate (III)
22. [PtCl3(SnCl3)]2–  Trichlorido trichlorostannitoplatinate(II)ion
23. Na3[Co(NO2)6]  Sodium hexanitrito–N cobaltate(III)
24. [PtCl4(NH3)2]  Diamminetetrachloridoplatinum (IV)
25. [PtCl2(NH3)4] [PtCl4]  Tetraamminedichloridoplatinum (IV) tetrachloridoplatinate(II)
26. [PdI2(ONO)2(H2O)2]  Diaquadiiodidodinitrito–O palladium (IV)
27. [CoCl(ONO)(en)2]  Chlorobis(ethylenediamine) nitrito–O cobalt (II)
28. [CoCl2(en)2]2SO4  Dichloridobis (ethylenediamine) cobalt (III) sulphate
29. [Cr(CO)5(PPh3)]  Pentacarbonyltriphenylphosphinechromium (O)
30. Na2[Ni(EDTA)]  Sodium ethylenediaminetetraacetatonickelate (II)
4+

31.  Tetraammine cobalt (III) –amido –superoxido tetraammine cobalt (III) ion

OR –amido –superoxido bis {tetraammine cobalt (III)} ion

32. [Be4O(CH3COO)6]  Hexa –– acetato–4 – oxido –tetra beryllium(II)
33. [CuCl(H2O)4]Cl  Tetraquachloridocopper (II) chloride
34. [CoBr(H2O)(NH3)4](NO3)2  Tetraammineaquabromocobalt (III) nitrate
35. Na[B(NO3)4]  Sodium tetranitratoborate (III)
36. [Zn4O(CH3COO)6]  Hexa--acetato-4-oxido-tetrazinc (II)
37. [(C6H5)3PCl Pd Cl2 PdCl(C6H5)3P]
 Chlorotriphenyl phosphene palladium (II) di--chloridochlorido triphenyl phosphene palladium (II)
 di--chloridodichloridobis (triphenylphosphene) di palladium (II)
 di--chloridobis{chloridotriphenyl phosphene palladium (II)}
 bis {–chlorido chloridotriphenyl phosphene palladium (II)}

Rf
38. H2[PtCl6]  Hexacloro platinic (IV) acid
39. [(Cl3Sn)2RhCl2Rh(SnCl3)2]4— 
IV
SnCl2 + Cl–  SnCl3–
Stannous chloride trichlorostannito
 Bis(trichlorostannito) rhodate (I) di –chlorido bis(trichlorostannito) rhodate(I) ion
 Di––chloridotetrakis(trichlorostannito) dirhodate(I) ion
 Di––chlorido bis{bis(trichlorostannito) rhodate (I)}ion
40. Fe(CO)5  Pentacarbonyl iron (O)
41. Co2(CO)8  Octacarbonyl dicobalt (O)
42. K2[Cd(CN)4]  Potassium tetracyanidocadmate (II)
43. [CrCl2(H2O)4]Cl  Tetraaquodichloridochromium (III) chloride
44. Co[Hg(SCN)4]  Cobalt(II)tetrathiocyanato–S Mercurate(II)
45. [Ag(NH3)2]Cl  Diammine silver (I) chloride
46. K[SbCl5(C6H5)]  Potassium pentachloridophenylantimonate (V)
47. [RuBr2(NH3)4]NO3  Tetraamminedibromoruthenium (III) nitrate
48. [CoCl(NO3)(NH3)4] [Au(CN)2]  Tetraamminechloridonitratocobalt (III) dicyanidoaurate (I)
49. [PtCl(NO2)(en)(NH3)2] Cl2  Diamminechloridoethylenediaminenitrito–N platinum (IV) chloride
50. [Ni(CN)4]2—  Tetracyanidonickelate (II) ion
51. [(NH3)5Cr-OH-Cr(NH3)5]Cl5
 Pentaammine chromium (III) –hydroxo pentaammine chromium (III) chloride
 –hydroxo bis {pentaammine chromium (III)}chloride

52. [Br2Pt(SMe2)2PtBr2] 

(Me2O  dimethyl ether/ Me2S Dimethyl thioehter)

 Dibromoplatinum (II) bis(-dimethyl thioether) dibromoplatinum (II)
 Bis{-dimethylthioether dibromo platinum (II)}
 bis(-dimethyl thioether) tetrabromo diplatinum (II)
53. [PtCl2(Et3P)2]  Dichloridobis (triethylphosphine) platinum (II)
54. [CuCl2(Et2NH)2]  Dichloridobis (diethylamine) copper (II)
55. [CoCl2(en)2]Cl  Dichloridobis (ethylenediamine) cobalt (III) chloride
56. K[PtCl3(C2H4)]  Potassium trichlorido-2-ethylene platinate (II)
57. K2[OsCl5N]  Potassium pentachloridonitridoosmate (VI)
58. Na3[Ag(S2O3)2]  Sodium bis(thiosulphato)argentate (I)
59. Na2[Fe(CN)5(NO)]  Sodium pentacyanidonitrosonium ferrate (II)
[NO in +1 state proved by magnetic moment]
60. K3[Fe(CN)5(CO)]  Potassium carbonyl pentacyanidoferrate (II)
 4

As per old convention complex is written as

[M(–ve ligand) (neutral ligand) (+ve ligand)]n±

As per new convention ligands are written in alphabetical order

[M (ligands are arranged in alphabetical order)]n±
6 –1 –2 –1/0 / 2 0
(19) K 2 [Cr(CN)2 (O)2 ( O2 2)(NH3 )]2– (Old convention) Potassium amminedicyanidodioxidoperoxidochromate(VI)

3 –2 –1/ –2 0 0
(20) K 2 [Co(O)2 ( O2 )(NH3 )(O2 )2 ]2–(Oldconvention)Potassiumamminebis(dioxygen)dioxidosuperoxidocobaltate(III)

6
K 2 [Cr(NH3 )(CN)2 (O)2 (O 2 )]2– (New convention) Potassium amminedicyanidodioxidoperoxidochromate(VI)

3
K 2 [Co(NH3 )(O2 )2 (O)2 (O2 )]2 – (New convention)Potassiumamminebis(dioxygen)dioxidosuperoxidocobaltate(III)
122
IUPAC naming of bridging/polynuclear complex compounds :

4+
NH3 –1 NH3 NH3
NH3 O2

Cr+3
–1
mining
Cr+3

NH3

Qamide
NH2 NH3
NH3 NH3

(1) Tetraamminechromium(III)--amido--superoxidotetraamminechromium(III) ion.

(2) -amido--superoxido octaammine dichromium(III) ion.
(3) -amido--superoxido bis{tetraamminechromium(III)} ion.

4+
diamine –1
OH
Bis ethylene 3+
(en)2 Co
3+
Co(en)2
troxide
HE
–1
OH

E
(1) bis(ethylenediamine)cobalt(III)di--hydroxidobis(ethylenediamine)cobalt(III)ion.
(2) di--hydroxido tetrakis(ethylenediamine)dicobalt(III)ion
(3) di--hydroxido bis{bis(ethylenediamine)cobalt(III)}ion
(4) bis{-hydroxidobis(ethylenediamine)cobalt(III)}ion

+2 2– – 0 +2 2– – 0
[Be4 (O )(CH3COO )6] [Zn4 (O )(CH3COO )6]
+2 +2
Be Zn
Ac Ac Ac Ac
Ac +2 Ac +2
+2 Be O Be +2 Zn O Zn
Ac Ac
Ac Ac Ac Ac
+2 Be +2 Zn
(Common name : Basic Beryllium Acetate) (Common name : Basic Zinc Acetate)
IUPAC name : Hexa--acetato--oxido tetraberyllium(II) IUPAC name : Hexa--acetato--oxido tetrazinc(II)

Note : Adjacent donor site of chelating ligand always occupy adjacent position of geometry.
 Bea CMW

E Bet
Basic Beryllining
acetate
BE

M atato
I oxidefraberyllium
Ma

1 is
palladium
II dichloride
g riphenylphosphiE.pephengephosphine
panadiumIT
triphenylphosphine
dipally
dim chlorido diadoro Bis
palladium
chloro triphenylphosphine
di M chloride Bis phosphine palladium
chlow triphenyl
Bis M chlorido
Text Example - 1 : I.U.P.A.C. name of the following complex Compounds :
1. K2[HgI4]  Potassium tetraiodidomercurate (II)
2. LiAlH4  Lithium tetrahydridoaluminate (III)
3. K3[Fe(CN)6]  Potassium hexacyanidoferrate (III)
4. K2[Pt Cl6]  Potassium hexachloridoplatinate (IV)
5. [PtCl2(NH3)2]  Diamminedichloridoplatinum (II)
6. [Co(NH3)6]Cl3  Hexaamminecobalt (III) chloride
7. [Fe(en)3]Cl3  Tris (ethylenediamine) iron (III) chloride
8. K3[Ir(C2O4)3]  Potassium trisoxalatoiridate (III)
9. [Co(NCS)(NH3)5]Cl2  Pentaammineisothiocyanato cobalt (III) chloride
Pentaamminethiocyanato–N–cobalt (III) chloride
10. [CoBr(ONO)(en)2]+1  Bromidobis(ethylenediamine) nitrito-O cobalt (III) ion
11. K2[Mo(CN)6]  Potassium hexacyanidomolybdate (IV)
12. [CoI(NH3)5]SO4  Pentaammineiodidocobalt (III) sulphate
13. [Co(NH3)6] [Co(ONO)6]  Hexaammine cobalt (III) hexanitrito–Ocobaltate (III)
14. (NH4)2[Pt(SCN)6]  Ammonium hexathiocyanato–S platinate (IV)
15. [Co(NO2)3(NH3)3]  Triamminetrinitrito-N-cobalt (III)
16. (NH4)3[Cr(NCS)6]  Ammonium hexaisothiocyanatochromate (III)
17. [Pt(NH3)4][PtCl4]  Tetraammine Platinum (II) tetrachloridoplatinate (II)
18. (NH4)4[Mo(CN)8]  Ammonium octacyanidomolybdate (IV)
19. [FeF6]3 –  Hexafluoridoferrate (III) ion
20. [CoCO3(NH3)5]Cl  Pentaamminecarbonatocobalt (III) chloride
21. K3[Fe(NH2)6]  Potassium hexaamidoferrate (III)
22. [PtCl3(SnCl3)]2–  Trichlorido trichlorostannitoplatinate(II)ion
23. Na3[Co(NO2)6]  Sodium hexanitrito–N cobaltate(III)
24. [PtCl4(NH3)2]  Diamminetetrachloridoplatinum (IV)
25. [PtCl2(NH3)4] [PtCl4]  Tetraamminedichloridoplatinum (IV) tetrachloridoplatinate(II)
26. [PdI2(ONO)2(H2O)2]  Diaquadiiodidodinitrito–O palladium (IV)
27. [CoCl(ONO)(en)2]  Chlorobis(ethylenediamine) nitrito–O cobalt (II)
28. [CoCl2(en)2]2SO4  Dichloridobis (ethylenediamine) cobalt (III) sulphate
29. [Cr(CO)5(PPh3)]  Pentacarbonyltriphenylphosphinechromium (O)
30. Na2[Ni(EDTA)]  Sodium ethylenediaminetetraacetatonickelate (II)
4+

31.
3 3  Tetraammine cobalt (III) –amido –superoxido tetraammine cobalt (III) ion

I
OR –amido –superoxido bis {tetraammine cobalt (III)} ion
32. [Be4O(CH3COO)6]  Hexa –– acetato–4 – oxido –tetra beryllium(II)
33. [CuCl(H2O)4]Cl  Tetraquachloridocopper (II) chloride
34. [CoBr(H2O)(NH3)4](NO3)2  Tetraammineaquabromocobalt (III) nitrate
35. Na[B(NO3)4]  Sodium tetranitratoborate (III)
36. [Zn4O(CH3COO)6]  Hexa--acetato-4-oxido-tetrazinc (II)
37. [(C6H5)3PCl Pd Cl2 PdCl(C6H5)3P]
 Chlorotriphenyl phosphene palladium (II) di--chloridochlorido triphenyl phosphene palladium (II)
 di--chloridodichloridobis (triphenylphosphene) di palladium (II)
 di--chloridobis{chloridotriphenyl phosphene palladium (II)}
 bis {–chlorido chloridotriphenyl phosphene palladium (II)}

Rf
38. H2[PtCl6]  Hexacloro platinic (IV) acid
39. [(Cl3Sn)2RhCl2Rh(SnCl3)2]4— 
IV triallonstannite
SnCl2 + Cl–  SnCl3–
Stannous chloride trichlorostannito
 Bis(trichlorostannito) rhodate (I) di –chlorido bis(trichlorostannito) rhodate(I) ion
 Di––chloridotetrakis(trichlorostannito) dirhodate(I) ion
 Di––chlorido bis{bis(trichlorostannito) rhodate (I)}ion
40. Fe(CO)5  Pentacarbonyl iron (O)
41. Co2(CO)8  Octacarbonyl dicobalt (O) NOT
42. K2[Cd(CN)4]  Potassium tetracyanidocadmate (II)
43. [CrCl2(H2O)4]Cl  Tetraaquodichloridochromium (III) chloride
44. Co[Hg(SCN)4]  Cobalt(II)tetrathiocyanato–S Mercurate(II)
45. [Ag(NH3)2]Cl  Diammine silver (I) chloride
46. K[SbCl5(C6H5)]  Potassium pentachloridophenylantimonate (V)
47. [RuBr2(NH3)4]NO3  Tetraamminedibromoruthenium (III) nitrate
48. [CoCl(NO3)(NH3)4] [Au(CN)2]  Tetraamminechloridonitratocobalt (III) dicyanidoaurate (I)
49. [PtCl(NO2)(en)(NH3)2] Cl2  Diamminechloridoethylenediaminenitrito–N platinum (IV) chloride
50. [Ni(CN)4]2—  Tetracyanidonickelate (II) ion
51. [(NH3)5Cr-OH-Cr(NH3)5]Cl5
 Pentaammine chromium (III) –hydroxo pentaammine chromium (III) chloride
 –hydroxo bis {pentaammine chromium (III)}chloride

52. [Br2Pt(SMe2)2PtBr2] 

(Me2O  dimethyl ether/ Me2S Dimethyl thioehter)

 Dibromoplatinum (II) bis(-dimethyl thioether) dibromoplatinum (II)
 Bis{-dimethylthioether dibromo platinum (II)}
 bis(-dimethyl thioether) tetrabromo diplatinum (II)
53. [PtCl2(Et3P)2]  Dichloridobis (triethylphosphine) platinum (II)
54. [CuCl2(Et2NH)2]  Dichloridobis (diethylamine) copper (II)
55. [CoCl2(en)2]Cl  Dichloridobis (ethylenediamine) cobalt (III) chloride
56. K[PtCl3(C2H4)]  Potassium trichlorido-2-ethylene platinate (II)
57. K2[OsCl5N]  Potassium pentachloridonitridoosmate (VI)
58. Na3[Ag(S2O3)2]  Sodium bis(thiosulphato)argentate (I)
59. Na2[Fe(CN)5(NO)]  Sodium pentacyanidonitrosonium ferrate (II)
[NO in +1 state proved by magnetic moment]
60. K3[Fe(CN)5(CO)]  Potassium carbonyl pentacyanidoferrate (II)
Text Example - 2 : I.U.P.A.C. name of the following complex Compounds :
1. [ Ni (CO ) 2 ( PPh 3 ) 2 ]  Dicarbonyl bis(triphenylphosphine) nickel (O)
2. [(en)2Co(NH2)(OH)Co(en)2]4+  Bis(ethylenediamine) cobalt(III) –amido –hydroxo
bis(ethylenediamine) cobalt(III) ion
3. [(CO)3Fe(CO)3Fe(CO)3]  Tri--carbonyl–bis(tricarbonyl iron (O))
4. [(NH3)5CrOHCr(NH3)4(H2O)]5+  Pentaammine chromium (III) –hydroxotetraammine aquo
chromium(III) ion
5. [CoN3(NH3)5]SO4  Pentaammineazidocobalt (III) sulphate
6. [Co(NH2)2(NH3)4]OC2H5  Diamidotetraamminecobalt(III) ethoxide
7. [Pt(Cl)(NO2)(NH3)4]SO4  Tetraamminechloronitrito–N platinum (IV) sulphate
8. [CrCl2(H2O)4]Cl  Tetraaquodichlorochromium (III) chloride
9. [Ru(N3)(NH3)5]Cl2  Pentaammineazidoruthenium(III) chloride
10. [CoCl3(NH3)3]  Triamminetrichlorocobalt(III)
11. [PtCl4(NH3)2]  Diamminetetrachloroplatinum (IV)
12. [CrCl(H2O)5]Cl2  Pentaaquachlorochromium(III) chloride
13. Ti(-c5H5)2(-C5H5)2  Bis(cyclopentadienyl) bis 5-cyclopentadienyl titanium (IV)

14. Mo(-C3H5)(-C5H5)(CO)3  Allyl tricarbonyl- 5 – cyclopentadienyl molybdum (II)

CH2=CH–CH2(–) allyl

15. Mn(-C5H5)(CO)3  Tricarbonyl- 5 – cyclopentadienyl manganese (I)

16. Cr(C6H6)(CO)3  6 –benzene tricarbonyl chromium (O)

17. Fe(CO)2(-C5H5)(-C5H5)  Dicarbonyl- 5 –cyclopentadienyl cyclopentadienyl iron (II)

18. Cr(C6H6)2  Bis ( 6 –benzene) chromium (O)

19. Fe(-C5H5)2  Bis ( 5 –cyclopentadienyl) iron (II)

20. Mn(CO)5(-C3H5) or Mn(CO)5(–CH2–CH=CH2)  Allyl pentacarbonyl manganese (I)

21. Co(CO)3(-C3H5)  3 –allyl tricarbonylcobalt (I)

22. Fe(  C4H4 )(CO)3  tricarbonyl-4-cyclobutadiene iron (O)
23. [PtCl2(NH3)(C2H4)]  Amminedichloro (2 – ethylene) platinum (II)
24. Ni(CO)4  Tetracarbonylnickel (O)
25. Mn2(CO)10  Decacarbonyl dimanganese (O)
26. [Cu(NH3)4][PtCl4]  Tetraaminecopper (II) tetrachloro platinate (II)
27. [W(en)3]Cl3  Tris (ethylenediamine) tungston (III)chloride
28. K3[Co(NCS)6]  Potassium hexathiocyanato–N cobaltate (III)
29. [Pt(NH3)4][Cr(NCS)(NO2)2(NH3)2Py]  Tetrammine platinum (II) diammine dinitrito-N
pyridine thiocyanato-N chromate (I)
30. K3[Co(C2O4)2Cl2]  Potassium dichlorobis(oxalato)cobaltate (III)
31.  Tetraamine cobalt (III) di––hydroxo bis (ethylenediamine) cobalt

(III) chloride {III way is not applicable}

32. Na2[Pt(CN)2I(NO2)]  Sodium dicyanidoiodidonitrito-N-platinate (II)
33. [Ru(PPh3)3Cl3]  Trichlorotris(triphenylphosphine)ruthenium(III)
34. K2[Co(N3)4]  Potassium tetraazidocobaltate (II)
35. [NiCl2(Ph3P)2]  Dichlorobis(triphenylphosphine) nickel (II)
36. [Cr(acac)3]  Tris(acetylacetanato) chromium (III)
37. [IrCl(CO)(Ph3P)2]  Carbonylchlorobis(triphenylphosphine) iridium (I)
38. [Co(NCS)(NH3)5]Cl2  Pentaammine thiocyanato–N cobalt (III) chloride
39. [Pt(C5H5N)4] [PtCl4]  Tetrapyridine platinum (II) tetrachloroplatinate (II)
40. [CrCl(ONO)(NH3)4] NO3  Tetraammine chloronitrito-O-chromium (III) nitrate
41. [Co(NH3)6][CuCl5]  Hexaamminecobalt (III) pentachlorocuprate (II)
42. [Ca(EDTA)]2—  Ethylenediaminetetraacetato calcate (II) ion
43. [Fe(H2O)5(NO)]SO4  Pentaaquanitrosonium iron (I) sulphate
[brown ring complex is unstable]
44. K4[Ni(CN)4]  Potassium tetracyanidonickelate (O)
45. [Al(OH)(H2O)5]SO4  Pentaaquohydroxoaluminium (III) sulphate
46. [VBr2(H2O)(NH3)2]Br  Diammineaquodibromovanadium (III) bromide
47. Na[Co(CO)4]  Sodium tetracarbonylcobaltate (–I)
48. Fe4[Fe(CN)6]3  Iron (III) hexacyanidoferrate (II)
49. Fe3[Fe(CN)6]2  Iron (II) hexacyanidoferrate (III)
50. [Cr(en)3] [Ni(CN)5]  Tris (ethylenediamine) chromium (III) pentacyanido nickelate (II)
51. [(NH3)4CoNH2NO2Co(NH3)4](NO3)4 –amido –nitro bis {tetraammine cobalt (III)} nitrate
 Tetraammine cobalt (III) –amido –nitro tetraammine
cobalt (III) nitrate
 –amido –nitro–octamminedicobalt (III) nitrate
52. K[B(C2H5)4]  Potassium tetraethyl borate (III)
53. [PtBr(NH3)3] NO3  Triamminebromoplatinum (II) nitrate
54. trans-[PtCl2(NH3)2]  Trans–diammine dichloroplatinum (II)
55. [RhCl(PPh3)3]  Chlorotris (triphenylphosphine) rhodium (I)
56. [Ni(dmg)2]  Bis (dimethylglyoximato) nickel (II)
57. [Co(NH3)6][Cr(CN)6]  Hexaamminecobalt (III) hexacyanidochromate (III)
58. Ni(–C4H4)2  bis (4- cyclobutadiene) nickel (0)
59. [CoCl(NCS)(NH3)4]+  Tetraamminechlorothiocyanato–N cobalt (III) ion
60. [PtCl4(en)]  Tetrachloroethylenediamine platinum (IV)
61. [CoBrCl(en)(NH3)2] NO3  Diamminebromochloroethylenediamine cobalt (III) nitrate
 QUESTIONS FOR PRACTICE–4
Single Choice Questions :
1. Which of the following is correct IUPAC name of any complex compound.
(A) Tris (acetyl acetonato) iron (III) chloride
(B) Hexachloridoplatinum (IV) tetraammine dicyanido platinate (IV)
(C) Ammine bromidochlorido methylamine platinum (II)
(D) Cis dichlorido (ethylenediamine) platinum (II)

2. Correct IUPAC name of [Pd(NO3)2(en)2]3 [Cr(CN)6]2 is :

(A) Dinitratobis(ethylenediamine)palladium(IV)hexacyanidochromate(III)
(B) Bis(ethylenediamine)dinitratopalladium(IV)hexacyanidochromate(III)
(C) Bis(ethylenediamine)dinitrato-N-palladium(IV) hexacyanido chromate(III)
(D) Bis(ethylenediamine)dinitratopalladium(II)hexacyanido chromate(III)

3. Correct IUPAC name of complex compound [Co(NCS) (NH3)5] [Zn(CN)4]

(A) Pentaamminethiocyanato-N-cobalt (III) tetracyanidozinc(II).
(B) Pentaamminethiocyanato-S-cobalt (III) tetracyanidozincate(II).
(C) Pentaamminethiocyanato-N-cobalt(II) tetracyanidozincate(II).
(D) Pentaamminethiocyanato-N-cobalt(III) tetracyanidozincate(II).

One or more than one correct :

4. Find out correct I.U.P.A.C. name of complex compound
(A) Pentaamminecyanidochromium(II)hexanitrito-N-irridate(III)
(B) Triamminetricyanidochromium(III)hexanitrito-N-irridate(III)
(C) Hexanitrito-N-irridium(III)pentaamminecyanidochromate(II)
(D) Pentaamminecyanidochromium(III)hexanitrito-N-irridate(III)

5. Select complex(s) with their correct IUPAC name

(A) Fe[Fe(CN)6] Iron (III) hexacyanido ferrate (III)
(B) Fe2[Fe(CN)6] Iron (II) hexacyanido ferrate (II)
(C) Fe3[Fe(CN)6]2 Iron (II) hexacyanido ferrate (III)
(D) Fe4[Fe(CN)6]3 Iron (III) hexacyanido ferrate (II)

Match the column :

6. Column-I Column-II
(A) Hexabromidoplatinate (IV) ion (P) Monodentate ligand is present in complex ion
(B) Potassiumdiamminetetrabromidocobaltate (III) (Q) Negative ligand is present in complex ion
(C) Tris(ethylenediamine) copper (II) (R) Neutral ligand is present in complex ion
sulphate
(D) Hexacarbonylmanganese (I) (S) Central atom of complex ion is a member of
perchlorate 3d (first) transition series
(T) Six coordination number of central atom in
complex ion

__
Werner’s Theory of Coordination Compounds :
Werner was the first scientist who tried to explain bonding in complex compounds for that he did some
experiments with various samples of cobalt (III) complexes and expained his theory by giving following
postulates.
(1) In complex compounds, metal cation exhibit two type of valency
(a) Primary valency (oxidation state).
(b) secondary valency (coordination number).
(2) Primary valency is ionizable and secondary valency is non-ionizable.
(3) Every metal cation in complex compound has its fixed secondary valency.
(4) Primary valency is satisfied by –ve ions whereas secondary valency is satisfied either by –ve ions or by
neutral molecules. It means –ve ions may satisfy both type of valencies.
(5) Primary valency has non-directional character whereas secondary valency has directional character. Therefore,
a complex ion has its definite geometry.
3
CoCl3 .6NH3 + AgNO3 solution  3 moles of AgCl

(I)
CoCl3.5NH3 + AgNO3 solution  2 moles of AgCl
(II)
CoCl3.4NH3 + AgNO3 solution  1 mol of AgCl
(III)
CoCl3.3NH3 + AgNO3 solution  No ppt
(IV)
In all above complexes secondary valency of Co3+ is 6

Werner representation

Primary valency ( dotted line ) Secondary valency ( dash line )

–
Cl
NH3

(1)
NH3
Cl
–
Co
3+
NH3
Modern representation = [Co(NH3)6]Cl3
Number of Cl– ions precipitated = 3
PY
NH3 Total number of ions = 4 (one complex cation + 3Cl–)
NH3
NH3
–
Cl
Structure of Co(NH3)6 Cl3
(Werner representation)

NH3 3
(2)
NH3 NH3
Modern representation = [CoCl(NH3)5]Cl2
PV
Cl
–
Co
3+
Cl
–
Number of Cl– ions precipitated = 2 SV 6
NH3 NH3 Total number of ions = 3 (one complex cation + 2Cl–)
–
Cl
Structure of Co(NH3)5 Cl3
(Werner representation)

NH3 –
Cl– Cl
3+
(3) Cl– Co Modern representation = [CoCl2(NH3)4]Cl
NH3 NH3
–
Number of Cl ions precipitated = 1 )
NH3 –
Total number of ions = 2 (one complex cation + 1Cl
Structure of Co(NH3)4 Cl3
(Werner representation)
 NH3 –
Cl– Cl
+3
(4) Co Modern representation = [CoCl3(NH3)3]
NH3 –
NH3 Number of Cl ions precipitated = 0
Cl–
Total number of ions = 0
Structure of Co(NH3)3Cl3
(Werner representation)
Order of electrical conductance : 1 > 2 > 3 > 4 (more ions  more conductance)
Complex compound which gives maximum number of total ions in aqueous solution on ionization will have
maximum electrical conductance (charge carrying capacity of ions should be equal).

QUESTIONS FOR PRACTICE–5

Single Choice Questions :
1. A compound has the empirical formula CoCl3·5NH3. When an aqueous solution of this compound is mixed
with excess silver nitrate, 2 mol of AgCl precipitate per mol of compound. On reaction with excess HCl, no

NH 4 is detected. Hence, it is:

(A) [Co(NH3)5Cl2]Cl (B) [Co(NH3)5Cl]Cl2
(C) [Co(NH3)5Cl3] (D) [Co(NH3)4Cl2]Cl·NH3

2. Consider the molecular formula of following complexes.

(I) CoCl3.6NH3 (II) CoCl3.5H2O (III) CoCl3.4NH3
If number of coordinated neutral ligands in (I), (II) and (III) complexes are respectively 6, 5 and 4, then primary
valency of metal cation in (I), (II) and (III) respectively are :
(A) 6, 5, 4 (B) 3, 2, 1 (C) 0, 1, 2 (D) 3, 3, 3
3. If excess of AgNO3 solution is added to 100 mL of a 0.024 M solution of dichlorobis (ethylene diamine) cobalt
(III) chloride, how many mol of AgCl be precipitated:
(A) 0.0012 (B) 0.0016 (C) 0.0024 (D) 0.0048
4. Which of the following complexes has the least molar conductivity in the solution?
(A) CoCl3·3NH3 (B) CoCl3·4NH3
(C) CoCl3·5NH3 (D) CoCl3·6NH3

5. Excess AgNO3 solution was added to 100 ml of 0.1 M solution of CoBr3xNH3 and 0.02 moles yellow
coloured precipitate was obtained, then the correct formula of the given complex compound is :
(A) [CoBr2(NH3)4]Br (B) [CoBr(NH3)5]Br2
(C) [Co(NH3)6]Br2 (D) [CoBr2(NH3)4]Br.NH3
Comprehension (6-7)
Addition compounds which do not lose their identity in aqueous solution are called double salts and those
lose their identity in aqeous solution are called complex salts, species which are directly linked with central
metal atom / ion are called ligands. The ligands having two or more donor atoms are called polydentate or
multidentate ligands.
6. Which of the following complex compound is non-ionisable in aqueous solution?
(A) PtCl4 · 3NH3 (B) PtCl4 · 6NH3 (C) PtCl4 · 2NH3 (D) PtCl4 · 4NH3
7. (i) Complex (P) + AgNO3 soln.  White precipitate
(ii) Complex (Q) + BaCl2 soln.  White precipitate
(iii) Complex (R) + Na2SO4 soln.  White precipitate
Pick the most appropriate option
(A) Complex (P) may contain Cl– in coordination sphere but not in ionisation shpere
(B) Complex (Q) may contain Ag+ cation in coordination sphere but not in ionisation shpere
(C) Complex (R) may contain Ba2+ cation in ionisation sphere but not in coordination sphere
(D) Complex (Q) may contain SO42– ion in coordination sphere but not in ionisation shpere
Valency bond theory (VBT) :
According to VBT surrounding ligands form coordinate bond with the vacant orbital of central metal atom/ion.
These pure vacant orbitals equalise their energy by process of intermixing named as hybridisation.
Type of hybridisation, geometry and magnetic behaviour of complex compound depends upon nature of
ligands. When ligands are arranged in increasing order of their splitting power, then an experimentally
determined series is obtained, named as spectrochemical series.

Splitting power of ligand  electron donating & accepting tendency of ligand.

Spectrochemical series :

O
I– < Br– < SCN– < Cl– < S2– < NO3– < N3– < F– < OH– < CH3COO– < C2O42– < O2– < H2O (weak field lgds.)
< NCS– CH3CN < EDTA4– < NH3 < Py < en < dipy < Phen < NO2– < PPh3 < CN– < CO...(strong field lgds.)
Note : (i) EDTA4– is strong field ligand due to chelation. (forms stable 5 member ring with central metal atom / ion)
(ii) Strong field ligands (SFL), NCS–, EDTA4–, NH3, Py, en, dipy, phen, NO2–, CN–, CO are also named as low
spin ligands and hyper ligands.
(iii) Weak field ligands (WFL), I– < Br– < SCN– < Cl– < S2– < NO3– < N3– < F– < OH– < CH3COO– < C2O42– <
H2O are also named as high spin ligands and hypo ligands.

Postulates of Valency bond theory (VBT) :

(1) Strong field ligands like CN–/CO will form possible pair of unpaired electrons present in central metal
atom/ions. (SFL  Spin decreases of metal atom/ions).

(2) Weak field ligands like H2O/OH–, will have no effect on electronic configuration of central metal atom/ion.
(WFL  Spin remain constant of metal atom/ions)

(3) Complex compound with zero unpaired electrons is called diamagnetic (repelled by magnetic field) and
complex compound with at least one unpaired electron is called paramagnetic (attracted by magnetic field).

(4) If inner d-orbital are involved in hybridization, then it is named as inner orbital complex and when d-orbitals of
outer shell are involved in hybridization, then it is named as outer orbital complex (inner & outer term is
defined only w.r.t d-orbital).

Low spin complex

(spin decreases w.r.t isolated central metal atom (CMA) / ion)
+n
n+
(5) M + xL [MLx]y±
(Complex)
High spin complex
(spin increases w.r.t respective low spin complex)

µ z

2
6
Geometry of complex depends upon its coordinations number as follows :

C.N. Type of hybridization Molecular geometry Bond angle

180º
2 sp hybridization L M L 180º
Linear

M
3 sp2 hybridization 120º
120º
L L
Trigonal planar

4 sp3 / d3s hybridization (dxy,dyz,dzx)

M 109º28

L L
L
(Td geometry)

L L

M 90º
4 d x 2 – y 2 sp 2 hybridization 90º
L L
(square planar)

90º L
3 3
sp dz 2 hybridization dz 2sp hybridization L M 120º 120º (Eq. B.A.)
5 90º (Axial B.A.)
(Outer O.C.) (Inner O.C.) L
L
(Non regular TBP geometry)

3 3
L L
5 sp dx 2 – y2 hybridization dx 2 – y 2 sp hybridization 90º
M
(Outer O.C.) (Inner O.C.)
L L
(Square pyramidal geometry)

L L
3 2 2 3
sp d hybridization d sp hybridization M
6 90º
(Outer O.C.) (Inner O.C.) L L
(dx2 – y2 , dz2)
L
(Square bipyramidal/octahedron)
INORGANIC CHEMISTRY

NOTES

COORDINATION
COMPOUNDS
PART 4
 IQIIIt
1. [Fe2+(CN)6]4– (ferrocyanide ion) t
3d
6
4s 4p 4d – 4–
2+
CN
Fe : CN –
CN
–

–
CN is a strong field ligand (SFL), so it will pair up unpaired electrons Fe2+

3d
6
4s 4p 4d CN– CN–
2+ 4– –
[Fe (CN)6] : **** ** ****** CN
–
CN CN CN CN CN CN
– – – – –
(Octahedron geometry)
2 3
d sp hybridization (inner orbital complex)
- -
 = 0 , low spin complex , octahedron geometry
- - 3–
2. [Fe3+(CN)6]3– (Ferricyanide ion) CN
–

–
CN –
CN
5
3d 4s 4p 4d
Fe
3+
: Fe3+

I
CN– is a strong field ligand (SFL), so it will pair up unpaired electrons CN– –
CN–
CN

5
3d
6
4s 4p 4d
3+ 3– (Octahedron geometry)
[Fe (CN)6] : **** ** ******
– – – – – –
CN CN CN CN CN CN

FEB G
2 3
d sp hybridization (inner orbital complex)
-
 = 3 , low spin complex , octahedron geometry

Mmm 3d
8
4s 4p 4d
+2 2–
3. [NiCl4] : ** ******

(WFL) Cl– Cl– Cl– Cl–

3
sp hybridization , tetrahedral geometry
 = 8 (paramagnetic) , high spin complex

8
3d 4s 4p 4d
+2
4. [Ni(CN)4]
2–
: ** ** ****
– – – –
(SFL) CN CN CN CN
dsp2 hybridization , inner orbital complex
 = 0 (diamagnetic) , low spin complex,
square planar geometry

(8+2)
3d 4s 4p
5. [Ni(CO)4] : (CO is a S.F.L., 4s electron will be shifted to 3d orbital.)

(SFL)

10
d 4s 4p
** ******
CO CO CO CO
3
sp hybridization, Td geometry
 = 0 (diamagnetic) , Low spin complex

me
 3d 4s 4p
2–
6. [Fe(CO)4] : ** * ** ** *
CO COCO CO
(SFL)
sp3 hybridization, Td Geometry
 = 0 (diamagnetic), Low spin complex

3d
8
4s
0
4p0 4d0
2+ 2+
7. [Ni (H 2O) 6] (light green complex ion) : ** ****** ****

(WFL) H2O OH2 OH2OH2 OH2OH2

3 2
sp d hybridization (outer Orb. Complex)
octahedron geometry, M.M= 8 B.M
Low spin and high spin not defined

3d8 4s0 4p0 4d0

2+ 2+
8. [Ni (NH3)6] (Limitation of VBT) : ** ****** ****
NH3 NH3 NH3 NH3 NH3 NH3
(SFL)
3 2
sp d hybridization (outer Orb. Complex)
octahedron geometry, M.M= 8 B.M
Low spin and high spin not defined

Note :
(1) Octahedron complexes in which metal cation is having d1, d2, d3 configuration surrounded by six any type of
ligands always form stable inner orbital complex with d2sp3 hybridization and their magnetic moments are
3 , 8 and 15 respectively..

(2) Octahedron complexes in which metal cation is having d8, d9, d10 configuration surrounded by six any type
of ligands always form outer orbital complex with sp3d2 hybridization and their magnetic moments are 8 , 3
and 0 BM respectively.

(3) In all above octahedron complexes low spin and high spin term is not defined because spin of metal
atom / ion remains constant.

d8 d8 d8 d8 d8 d8
2
Ex. [ Ni (CN)4(en)] ; [ Ni 2
2– (H2O)6] ; [ Ni 2
2+ (NH3)6] ; [ Ni 2
2+ (en)3] ; [ Ni 2
+2 (NO2)6] ; [ Ni 2
4– (SCN)2(Py)2(NH3)2]

sp3d2 hybridization, (outer O.C.) Octahedron, M.M = 8 BM (LS and HS term not defined)

d3 d3 d3 d3 d3 d3
[ Cr 3  (H2O)6]3+ ; [ Cr 3  (acac)3]0 ; [ Cr 3  (CN)6]3– ; [ Cr 3  (NH3)6]3+ ; [ Cr 3  Cl2(NH3)2(NO2)2]– ; [ Cr Cl2(NH3)4]+

d2sp3 hybridization, (inner O.C.) Octahedron, M.M = 15 BM (L.S & HS term not defined)
 3d3 4s0 4p0 4d0
3+
3–
9. [Cr(CN)6] (Limitation of VBT) : **** ** ******
CN CN CN CNCNCN
(SFL)
d2sp3 (hybridization (inner O.C.)
Octahedron , M.M= 15 B.M (LS and HS not defined)
0 0
3d
3
4s
0
4p 4d
3+
3+
10. [Cr(H2O)6] (violet colour complex ion) : **** ** ******
H2OH2O H2O H2O H2OH2O
(WFL)
d2sp3 (hybridization (inner O.C.)
Octahedron, M.M= 15 B.M (LS and HS not defined)
0 0
3d
1
4s
0
4p 4d
11. +3
[Ti (H 2O) 6]
3+
(Limitation of VBT) : **** ** * ** ** *
H2OH2O H2O H2O H2OH2O
(WFL)
d2sp3 (Inner orbital complex)
Octahedron, = 3 B.M (LS and HS not defined)

0 0
3d9 4s 4p
12. +2 2–
[Cu X4] (X = Cl , Br )
– –
: ** ******
– – – –
X X X X
(WFL)
sp3 Hybridization, Td. geometry
M.M= 3 B.M (HS and LS not defined)

[CuX4]2– ; [Cu(SCN)4]2– ; [Cu(H2O)4]2+ ; [Cu(ONO)4]2–

Td geometry, sp3 hybridization,  = 3 BM

(Low spin/high spin not defined)

Condition for transference (not promotion) of only one unpaired electron :

(1) Metal cation must be surrounded by all strong field ligands.
(2) After transference of only one unpaired electron, stable inner orbital complex must be formed.
Both above conditions must be satisfied simultaneously.

Inner orbital complex (stability) > Outer orbital complex (stability)

13. [Cu+2(NH3)4]+2 SFL (Deep blue colour complex) required to be square planar
3d 4s 4p 4d

dx2–y2
** ** * ** *
NH3 NH3 NH3 NH3
2
dsp (Inner orbital complex)
square planar
 = 3 BM
Unpaired electron is present
in 4p orbital rather than in 3d
orbital
[Cu+2(NH3)4]2+, [Cu+2(NO2)4]2– ; [Cu+2(en)2]2+ ; [Cu+2(py)4]2+ ; [Cu+2(CN)2(NO2)2]2–

(Unpaired electron is present in 4p instead of 3d).

Square planar geometry, dsp2, inner orbital complex, low / high spin not defined,  = 3 B.M
 3d6 4s0 4p0 4d0
+2 2+
14. [Co (NH3)6 ] **** ** ******
SFL
NH3 NH3 NH3 NH3 NH3 NH3
2 3
d sp hybridization

M.M = 3 BM (Inner orbital / low spin complex)

[Co+2(CN)6]4–, [Co+2(NH3)6]+2, [Co+2(en)3]2+, [Co+2(py)2(NO2)4]2–, [Co(py)2(NH3)2(CN)2]0

(octahedron, d2sp3, inner orbital, low spin,  = 3 BM )

All these complex compounds can act as reductant by removal of 4d electron because unpaired electron is
present in 4d rather 3d orbital.

IMPORTANT POINT :

–e–
• [Co2+(NH3)6]2+ (less stable) [Co3+(NH3)6]3+ (more stable)
Oxidation

(act as reducing agent by removing one electron

from 4-d orbital lying at higher energy level)

• [Cu2+(NH3)6]2+ (more stable) [Cu3+(NH3)4]3+ (less stable) [Cu2+(stability) > Cu3+(stability)]

(never act as reducing agent)

3d8 2–
[NiCl4]
s2
(paramagnetic)
p6 18
sp3
hybridization (Td) = 8 BM (high spin)
Poor shielding d10 4d8 2–
[PdCl4]
s2
p6 32 Dimagnetic/dsp2 hybridization (sq planar)/=0(L.S complex)
10
d 8
5d 2–
Very poor f
14
[PtCl4] L
shielding
dsp2 hybridization planar/=0

Note : • Zeff on valence shell of metal cation increases down the transition series.
• Complex compound in which metal cation is either of second or third transition series usually form
stable inner orbital complex irrespective of nature of ligand due to higher zeff on valence shell of metal
atom/ion.

Limitations of VBT :
(1) Experimental magnetic moment of all complex compounds cannot be explained by VBT.
(2) Colour of complex compound due to d-d transition cannot be explained by VBT.
 QUESTIONS FOR PRACTICE–6
Single Choice Questions :
1. [Ni(CN)4]2– and [NiCl4]2– have similarity but not in
(A) magnetic moment (B) C.N. and O.N. (C) structure (D) both (A) and (C)

2. Among Ni(CO)4, [Ni(CN)4]2– and NiCl24 ,

(A) Ni(CO)4 and [Ni(CN)4]2– are diamagnetic and NiCl24 is paramagnetic

(B) Ni(CO)4 and NiCl24 are diamagnetic and [Ni(CN)4]2– is paramagnetic

(C) Ni(CO)4 is diamagnetic and [Ni(CN)4]2– and NiCl24 are paramagnetic

(D) NiCl24 and [Ni(CN)4]2– are diamagnetic and Ni(CO)4 is paramagnetic.

3. Which of the following complex is an outer orbital complex ?

(A) [Ni(NH3)6]2+ (B) [Mn(CN)6]4– (C) [Co(NH3)6]3+ (D) [Fe(CN)6]4–

4. In which of the following complex ion the value of magnetic moment (spin only) is 3 BM and outer
d-orbitals is used in hybridization.
(A) [Mn(CN)6]4– (B) [Fe(NH3)6]3+ (C) [Co(CO)4] (D) [Cu(H2O)6]2+

5. Which of the following contains one unpaired electron in the 4p orbitals

(A) [Cu(NH3)2]+ (B) [Cu(NH3)4]2+ (C) [Cu(CN)4]3– (D) [Ni(CN)4]2–

6. Statement-1 : Ni(CO)4 complex has no unpaired electrons.

Statement-2 : 4s electrons of Ni atom enter into the inner d orbitals to facilitate the dsp2 hybridization
in Ni atom.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.

7. Statement-1 : Hund’s rule violates in [Co(CN)6]3– complex ion

Statement-2 : Degeneracy of d orbitals is lost under any field ligand.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.

Comprehension (Q.8 to Q.10)

The magnetic property, dipole moment, plane of symmetry, colour and absorption band can be helpful in
structure elucidation of complex compounds.
8. Which of the following complex ion is expected to absorb light in 4000Å to 7800 Å region. (visible region)
(A) [Ti(en)3]4+ (B) [Cr(H2O)6]3+
(C) [Sc(NH3)4(H2O)2]3+ (D) [Zn(en)2(NH3)2]2+

9. Pair of complexes, which do not have equal number of unpaired electron(s).

(A) [Co(CO)4]–, [Ni(CN)4]4– (B) [Co(H2O)6]3+, [NiF6]2–
(C) [Ni(en)3]2+[Cr(CN)6]4– (D) [Co(CN)6]4–, [Cr(NH3)6]3+

10. The cyano complex that exhibit highest value of paramagnetism is :

(B) [Co( CN)6 ]3 

3–
(A) [Mn (CN) 6 ] 4  (C) [Fe(CN)6 ] (D) [Cr (CN) 6 ]3 –
One or more than one correct :
11. Which one of the following statement(s) is/are false?
(A) Weak ligands like F—, Cl— and OH— usually form low spin complexes.

(B) Strong ligand like CN— and NO 2– , generally form high spin complexes.
(C) [FeF6]3– is high spin complex. (D) [Ni(CO)4] is high spin complex

12. dx2  y2 orbital of inner shell is used in the hybridization of :

(A) [Cu(NH3)4]2+ (B) [Ni(CN)5]3– (C) Fe(CO)5 (D) None

13. For which of the following dn configuration of octahedral complex (es), can not exist in both high spin and low
spin forms.
(A) d3 (B) d5 (C) d6 (D) d8

Match the Column :

14. Column-I Column-II

(Pair of complex compounds) (Property which is different in given pair)
(A) [Ni(CO)4] and K2[Ni(CN)4] (P) Magnetic moment
(B) [Cu(NH3)4]SO4 and K3[Cu(CN)4] (Q) Oxidation no. of central metal
(C) K2[NiCl4] and K4[Ni(CN)4] (R) Geometry
(D) K2[NiCl4] and K2[PtCl4] (S) EAN of central metal

Subjective :
15. Find out total number of paramagnetic inner orbital complex
K2[NiCl 4], K3[Fe(CN)6], K3[Cr(CN)6], K2[PtCl 4], Na2[Fe(CN)5NO], [Fe(H2O)5NO]SO 4, K3[Co(C2O 4)3],
K4[Co(CN)6], [Cu(NH3)4]SO4.

16. If x and y are total number of electrons which are present in non axial and axial set of d-orbitals respectively
2x 2
in Ni cation of [Ni(DMG)2], then calculate value of
y

17. Find out number of electron(s) in inner shell axial orbitals of central metal cation in complex [Co(NH3)6]2+

18. Consider the following reaction

Na / liq. NH3
K2[Ni(CN)4] K4[Ni(CN)4]
R.A.
(A) (B)

Find the change in magnetic moment from complex (A) to complex (B).
 PRACTICE–4

1. C 2. B 3. D 4. AD 5. ABCD
6. A  P,Q,T; B  P,Q,R,S,T; C  R,S,T; D P,R,S,T;

PRACTICE–5 __
1. B 2. D 3. C 4. A 5. B 6. C 7. C

PRACTICE–6

1. D 2. A 3. A 4. D 5. B 6. C 7. D
8. B 9. D 10. D 11. ABD 12. AB 13. AD
14. (A)  Q, R, S; (B)  P, Q, R, S; (C)  P, Q, S; (D)  P, R, S
15. 4 16. 36 17. 0 18. 0
INORGANIC CHEMISTRY

NOTES

COORDINATION
COMPOUNDS
PART 4
 IQIIIt
1. [Fe2+(CN)6]4– (ferrocyanide ion) t
3d
6
4s 4p 4d 4–
2+
CN–
Fe : CN –
CN
–

–
CN is a strong field ligand (SFL), so it will pair up unpaired electrons Fe2+

3d
6
4s 4p 4d CN– CN–
2+ 4– –
[Fe (CN)6] : **** ** ****** CN
–
CN CN CN CN CN CN
– – – – –
(Octahedron geometry)
2 3
d sp hybridization (inner orbital complex)
- -
 = 0 , low spin complex , octahedron geometry
- - 3–
2. [Fe3+(CN)6]3– (Ferricyanide ion) CN–
Boost CN
–

5
CN–
3d 4s 4p 4d
Fe
3+
: Fe3+

I
CN– is a strong field ligand (SFL), so it will pair up unpaired electrons CN– CN–
CN–

5
3d
6
4s 4p 4d
3+ 3– (Octahedron geometry)
[Fe (CN)6] : **** ** ******
– – – – – –
CN CN CN CN CN CN

FEB G
2 3
d sp hybridization (inner orbital complex)
-
 = 3 , low spin complex , octahedron geometry

Mmm 3d
8
4s 4p 4d
+2 2–
3. [NiCl4] : ** ******

(WFL) Cl– Cl– Cl– Cl–

sp3 hybridization , tetrahedral geometry
 = 8 (paramagnetic) , high spin complex

8
3d 4s 4p 4d
+2
4. [Ni(CN)4]
2–
: ** ** ****
– – – –
(SFL) CN CN CN CN
dsp2 hybridization , inner orbital complex
 = 0 (diamagnetic) , low spin complex,
square planar geometry
t ese

(8+2)
3d 4s 4p
5. [Ni(CO)4] : (CO is a S.F.L., 4s electron will be shifted to 3d orbital.)

(SFL)

10
d 4s 4p
** ******
CO CO CO CO
sp3 hybridization, Td geometry
 = 0 (diamagnetic) , Low spin complex

me
 3d 4s 4p
2–
6. [Fe(CO)4] : ** * ** ** *
CO COCO CO
(SFL)
sp3 hybridization, Td Geometry
 = 0 (diamagnetic), Low spin complex

3d8 4s0 4p0 4d0

2+ 2+
7. [Ni (H 2O) 6] (light green complex ion) : ** ****** ****

(WFL) H2O OH2 OH2OH2 OH2OH2

3 2
sp d hybridization (outer Orb. Complex)
octahedron geometry, M.M= 8 B.M
Low spin and high spin not defined

3d8 4s0 4p0 4d0

2+ 2+
8. [Ni (NH3)6] (Limitation of VBT) : ** ****** ****
NH3 NH3 NH3 NH3 NH3 NH3
(SFL)
3 2
sp d hybridization (outer Orb. Complex)
octahedron geometry, M.M= 8 B.M
Low spin and high spin not defined

Note :
(1) Octahedron complexes in which metal cation is having d1, d2, d3 configuration surrounded by six any type of
ligands always form stable inner orbital complex with d2sp3 hybridization and their magnetic moments are
3 , 8 and 15 respectively..

(2) Octahedron complexes in which metal cation is having d8, d9, d10 configuration surrounded by six any type
of ligands always form outer orbital complex with sp3d2 hybridization and their magnetic moments are 8 , 3
and 0 BM respectively.

(3) In all above octahedron complexes low spin and high spin term is not defined because spin of metal
atom / ion remains constant.

d8 d8 d8 d8 d8 d8
2
Ex. [ Ni (CN)4(en)] ; [ Ni 2
2– (H2O)6] ; [ Ni 2
2+ (NH3)6] ; [ Ni 2
2+ (en)3] ; [ Ni 2
+2 (NO2)6] ; [ Ni 2
4– (SCN)2(Py)2(NH3)2]

sp3d2 hybridization, (outer O.C.) Octahedron, M.M = 8 BM (LS and HS term not defined)

d3 d3 d3 d3 d3 d3
[ Cr3 (H2O)6] ; [ Cr 3 
3+ (acac)3] ; [ Cr 3 
0 (CN)6] ; [ Cr 3 
3– (NH3)6] ; [ Cr 3 
3+ Cl2(NH3)2(NO2)2]– ; [ Cr Cl2(NH3)4]+

d2sp3 hybridization, (inner O.C.) Octahedron, M.M = 15 BM (L.S & HS term not defined)
 3d3 4s0 4p0 4d0
3+
3–
9. [Cr(CN)6] (Limitation of VBT) : **** ** ******
CN CN CN CNCNCN
(SFL)
d2sp3 (hybridization (inner O.C.)
Octahedron , M.M= 15 B.M (LS and HS not defined)
0 0
3d
3
4s
0
4p 4d
3+
3+
10. [Cr(H2O)6] (violet colour complex ion) : **** ** ******
H2OH2O H2O H2O H2OH2O
(WFL)
d2sp3 (hybridization (inner O.C.)
Octahedron, M.M= 15 B.M (LS and HS not defined)
0 0
3d
1
4s
0
4p 4d
11. +3
[Ti (H 2O) 6]
3+
(Limitation of VBT) : **** ** * ** ** *
H2OH2O H2O H2O H2OH2O
(WFL)
d2sp3 (Inner orbital complex)
Octahedron, = 3 B.M (LS and HS not defined)

0 0
3d9 4s 4p
12. +2 2–
[Cu X4] (X = Cl , Br )
– –
: ** ******
– – – –
X X X X
(WFL)
sp3 Hybridization, Td. geometry
M.M= 3 B.M (HS and LS not defined)

[CuX4]2– ; [Cu(SCN)4]2– ; [Cu(H2O)4]2+ ; [Cu(ONO)4]2–

Td geometry, sp3 hybridization,  = 3 BM

(Low spin/high spin not defined)

Condition for transference (not promotion) of only one unpaired electron :

(1) Metal cation must be surrounded by all strong field ligands.
(2) After transference of only one unpaired electron, stable inner orbital complex must be formed.
Both above conditions must be satisfied simultaneously.

Inner orbital complex (stability) > Outer orbital complex (stability)

13. [Cu+2(NH3)4]+2 SFL (Deep blue colour complex) required to be square planar
3d 4s 4p 4d

dx2–y2
** ** * ** *
NH3 NH3 NH3 NH3
2
dsp (Inner orbital complex)
square planar
 = 3 BM
Unpaired electron is present
in 4p orbital rather than in 3d
orbital
[Cu+2(NH3)4]2+, [Cu+2(NO2)4]2– ; [Cu+2(en)2]2+ ; [Cu+2(py)4]2+ ; [Cu+2(CN)2(NO2)2]2–

(Unpaired electron is present in 4p instead of 3d).

Square planar geometry, dsp2, inner orbital complex, low / high spin not defined,  = 3 B.M
 3d6 4s0 4p0 4d0
14. [Co+2 (NH3)6 ]2+ **** ** ******
SFL
NH3 NH3 NH3 NH3 NH3 NH3
d2sp3 hybridization

M.M = 3 BM (Inner orbital / low spin complex)

[Co+2(CN)6]4–, [Co+2(NH3)6]+2, [Co+2(en)3]2+, [Co+2(py)2(NO2)4]2–, [Co(py)2(NH3)2(CN)2]0

(octahedron, d2sp3, inner orbital, low spin,  = 3 BM )

All these complex compounds can act as reductant by removal of 4d electron because unpaired electron is
present in 4d rather 3d orbital.

IMPORTANT POINT :

–e–
• [Co2+(NH3)6]2+ (less stable) [Co3+(NH3)6]3+ (more stable)
Oxidation

(act as reducing agent by removing one electron

from 4-d orbital lying at higher energy level)

• [Cu2+(NH3)6]2+ (more stable) [Cu3+(NH3)4]3+ (less stable) [Cu2+(stability) > Cu3+(stability)]

(never act as reducing agent)

3d8 2–
[NiCl4]
s2
(paramagnetic)
p6 18
sp3
hybridization (Td) = 8 BM (high spin)
Poor shielding d10 4d8 2–
[PdCl4]
s2
p6 32 Dimagnetic/dsp2 hybridization (sq planar)/=0(L.S complex)
10
d 8
5d 2–
Very poor f
14
[PtCl4] L
shielding
dsp2 hybridization planar/=0

Note : • Zeff on valence shell of metal cation increases down the transition series.
• Complex compound in which metal cation is either of second or third transition series usually form
stable inner orbital complex irrespective of nature of ligand due to higher zeff on valence shell of metal
atom/ion.

Limitations of VBT :
(1) Experimental magnetic moment of all complex compounds cannot be explained by VBT.
(2) Colour of complex compound due to d-d transition cannot be explained by VBT.
 QUESTIONS FOR PRACTICE–6
Single Choice Questions :
1. [Ni(CN)4]2– and [NiCl4]2– have similarity but not in
(A) magnetic moment (B) C.N. and O.N. (C) structure (D) both (A) and (C)

2. Among Ni(CO)4, [Ni(CN)4]2– and NiCl24 ,

(A) Ni(CO)4 and [Ni(CN)4]2– are diamagnetic and NiCl24 is paramagnetic

(B) Ni(CO)4 and NiCl24 are diamagnetic and [Ni(CN)4]2– is paramagnetic

(C) Ni(CO)4 is diamagnetic and [Ni(CN)4]2– and NiCl24 are paramagnetic

(D) NiCl24 and [Ni(CN)4]2– are diamagnetic and Ni(CO)4 is paramagnetic.

3. Which of the following complex is an outer orbital complex ?

(A) [Ni(NH3)6]2+ (B) [Mn(CN)6]4– (C) [Co(NH3)6]3+ (D) [Fe(CN)6]4–

4. In which of the following complex ion the value of magnetic moment (spin only) is 3 BM and outer
d-orbitals is used in hybridization.
(A) [Mn(CN)6]4– (B) [Fe(NH3)6]3+ (C) [Co(CO)4] (D) [Cu(H2O)6]2+

5. Which of the following contains one unpaired electron in the 4p orbitals

(A) [Cu(NH3)2]+ (B) [Cu(NH3)4]2+ (C) [Cu(CN)4]3– (D) [Ni(CN)4]2–

6. Statement-1 : Ni(CO)4 complex has no unpaired electrons.

Statement-2 : 4s electrons of Ni atom enter into the inner d orbitals to facilitate the dsp2 hybridization
in Ni atom.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.

7. Statement-1 : Hund’s rule violates in [Co(CN)6]3– complex ion

Statement-2 : Degeneracy of d orbitals is lost under any field ligand.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.

Comprehension (Q.8 to Q.10)

The magnetic property, dipole moment, plane of symmetry, colour and absorption band can be helpful in
structure elucidation of complex compounds.
8. Which of the following complex ion is expected to absorb light in 4000Å to 7800 Å region. (visible region)
(A) [Ti(en)3]4+ (B) [Cr(H2O)6]3+
(C) [Sc(NH3)4(H2O)2] 3+ (D) [Zn(en)2(NH3)2]2+

9. Pair of complexes, which do not have equal number of unpaired electron(s).

(A) [Co(CO)4]–, [Ni(CN)4]4– (B) [Co(H2O)6]3+, [NiF6]2–
2+
(C) [Ni(en)3] [Cr(CN)6]4– (D) [Co(CN)6]4–, [Cr(NH3)6]3+

10. The cyano complex that exhibit highest value of paramagnetism is :

(B) [Co( CN)6 ]3 

3–
(A) [Mn (CN) 6 ] 4  (C) [Fe(CN)6 ] (D) [Cr (CN) 6 ]3 –
One or more than one correct :
11. Which one of the following statement(s) is/are false?
(A) Weak ligands like F—, Cl— and OH— usually form low spin complexes.

(B) Strong ligand like CN— and NO 2– , generally form high spin complexes.
(C) [FeF6]3– is high spin complex. (D) [Ni(CO)4] is high spin complex

12. dx2  y2 orbital of inner shell is used in the hybridization of :

(A) [Cu(NH3)4]2+ (B) [Ni(CN)5]3– (C) Fe(CO)5 (D) None

13. For which of the following dn configuration of octahedral complex (es), can not exist in both high spin and low
spin forms.
(A) d3 (B) d5 (C) d6 (D) d8

Match the Column :

14. Column-I Column-II

(Pair of complex compounds) (Property which is different in given pair)
(A) [Ni(CO)4] and K2[Ni(CN)4] (P) Magnetic moment
(B) [Cu(NH3)4]SO4 and K3[Cu(CN)4] (Q) Oxidation no. of central metal
(C) K2[NiCl4] and K4[Ni(CN)4] (R) Geometry
(D) K2[NiCl4] and K2[PtCl4] (S) EAN of central metal

Subjective :
15. Find out total number of paramagnetic inner orbital complex
K2[NiCl 4], K3[Fe(CN)6], K3[Cr(CN)6], K2[PtCl 4], Na2[Fe(CN)5NO], [Fe(H2O)5NO]SO 4, K3[Co(C2O 4)3],
K4[Co(CN)6], [Cu(NH3)4]SO4.

16. If x and y are total number of electrons which are present in non axial and axial set of d-orbitals respectively
2x 2
in Ni cation of [Ni(DMG)2], then calculate value of
y

17. Find out number of electron(s) in inner shell axial orbitals of central metal cation in complex [Co(NH3)6]2+

18. Consider the following reaction

Na / liq. NH3
K2[Ni(CN)4] K4[Ni(CN)4]
R.A.
(A) (B)

Find the change in magnetic moment from complex (A) to complex (B).
 PRACTICE–4

1. C 2. B 3. D 4. AD 5. ABCD
6. A  P,Q,T; B  P,Q,R,S,T; C  R,S,T; D P,R,S,T;

PRACTICE–5 __
1. B 2. D 3. C 4. A 5. B 6. C 7. C

PRACTICE–6

1. D 2. A 3. A 4. D 5. B 6. C 7. D
8. B 9. D 10. D 11. ABD 12. AB 13. AD
14. (A)  Q, R, S; (B)  P, Q, R, S; (C)  P, Q, S; (D)  P, R, S
15. 4 16. 36 17. 0 18. 0
INORGANIC CHEMISTRY

NOTES

COORDINATION
COMPOUNDS
PART 5
 Crystal field theory (CFT)

L y±
L
L L L L

M M
L L L L External spherical field of
L surrounding legends over
L
Ionic interactions
I
metal cation

According to CFT, there are ionic interactions between metal and surrounding ligands. When ligands sur-
round the metal cation, then d-orbitals of central metal atom/ion are splitted into different energy levels due
to external field of surrounding ligands created over metal cation.

i orifice
Note :
Th
(1) Complex compound with C.N. = 4, in which first transition series metal cation/atom is surrounded by four
4
weak field ligands usually are in non-axial direction and geometry is tetrahedron.
If first transition series metal cation is surrounded by four strong field ligands, then they are usually in axial
direction, now geometry is square planar, except carbonyl complexes (CO lgds. are usually in non-axial
direction)

(2) Complex compound with C.N. = 5, in which first transition series metal cation is surrounded by five weak field
ligands, out of three of them are in non axial direction and two of them are in axial direction then the geometry
is usually trigonal bipyramidal.
When first T.S metal cation is surrounded by five strong field ligands, they are usually in axial direction now
geometry is square pyramidal except carbonyl complexes (CO ligands are usually in non axial direction).
e.g. Cr(CO)6 : Oct. geometry Fe(CO)5 : TBP geometry Ni(CO)4 : Td. geometry

(3) Complex compound in which metal cation is of either second or third T.S. then usually more stable inner
orbital complex is formed irrespective of nature of ligand due to high zeff on valence shell of metal cation (due
to large splitting)
e.g. [MCl4]2– (M = Pd2+, Pt2+ ) : square planar, dsp2 Hybridization, M.M. = 0 (L.S. complex)

(4) Complex compound in which metal cation is having oxidation state > +3 usually form stable inner orbital
complex irrespective of nature of ligand due to high zeff on valence shell of CMA / ion (due to large splitting).

(5) Octahedron complexes in which metal cation is having d1, d2, d3 configuration surrounded by six ligands
always form stable inner orbital complex irrespective of the nature of ligand due to high zeff on valence shell
of CMA / ion (due to large splitting of d-orbitals).

(6) Octahedron complexes in which metal cation is having d8, d9, d10 configuration surrounded by six any type
of ligands always form outer orbital complexes irrespective of nature of ligand.

A me
wager

p
>P
 10 3470 axis
2k
58 so Tigand

ii
His.int

octahedral

to
Is
to
I i It
FEE
tetrahedral non axial
f n

EI.ae
 Predict hybridization magnetic moment and geometry of following complexes :
dit
5 0 0 0
3d 4s 4p 4d
3–
(1) [MnBr5] 
WFL 3
sp dz2 Hyb
n

sp3dz2 Hybridization ,  = 35 , High spin , Geometry = TBP

9 0 0 0

3–
3d 4s 4p 4d P
(2) [CuCl5] 
WFL 3 n
sp dz 2 Hyb

sp3dz2 Hybridization ,  = 3 , Spin not defined , Geometry = TBP

8 0 0 0
3d 4s 4p 4d
3–
(3) [Ni(CN)5] 
SFL
2 n
dx2–y2 sp hyb

dx2–y2sp3 Hybridization ,  = 0 , Low spin , Geometry = square pyramidal

9 0 0 0
3d 4s 4p 4d
2+
(4) [Cu(NH 3)5] 
SFL dx2–y2 sp3hybridization

dx2–y2 sp3 Hybridization ,  = 3 , square pyramidal geometry,,

Low or high spin not defined (unpaired electrion is present in 4d orbital
rather 3d orbital)

(6+2) 0 0 0
3d 4s 4p 4d
0
(5) [Fe(CO) 5] 
SFL 3
dz2 sp hybridization

uxnii.id
dz 2 sp3 hybridization ,  = 0 , low spin complex , TBP geometry

Calculation of CFSE in octahedron field :

eg
+0.6'0 = 6Dq
neg eg
+0.60 = 6Dq
0' = 10Dq 0=10Dq
Oct. strong field ligand Oct. weak field ligand
+0.4'0 = –4Dq +0.40 = –4Dq

t2g mtg t2g

Filling of e–s in strong octahedron field. Filling of e–s in weak octahedron field.

CFSE (in strong oct. field) = –0.4 '0 × nt2g + 0.6 '0 × neg + xP (additional pairing energy)
CFSE (in weak oct. field) = –0.4 0 × nt2g + 0.60 × neg

_NEI___
 –2.40' CFSE(max)
–2.00'
CFSE(max) CFSE(max)
–1.20 –1.60'

–1.20'

–0.80'
–0.40
–0.40'

d0 d1 d2 d3 d4 d5 d6 d7 d8 d9 d10 d0 d1 d2 d3 d4 d5 d6 d7 d8 d9 d10
CFSE in weak octahedron field CFSE in strong field ligand

Calculation of CFSE in tetrahedron field :

t2g t2g
+0.4't +0.4t
't t
Td. strong field ligand Td. weak field ligand
–0.6't –0.6t

eg eg
Filling of e–s in strong tetrahedron field. Filling of e–s in weak tetrahedron field.

CFSE (in strong Td. field) = –0.6 't × neg + 0.4 't × nt2g+ xP (additional pairing energy)

CFSE (in weak Td. field) = –0.6 t × neg + 0.4t × nt2g

CFSE(max)
–2.4t'
CFSE(max) CFSE(max)
–1.20
–1.8t'

–1.2t'
–0.6t
–0.6t'

d0 d1 d2 d3 d4 d5 d6 d7 d8 d9 d10 d0 d1 d2 d3 d4 d5 d6 d7 d8 d9 d10
i
CFSE in weak Td. field CFSE in strong Td. field

Factors affecting CFSE of complex compound :

CFSE also determines stability of complex compound therefore, it also named as crystal field stabilisation
energy. It depends upon following factors
(1) Position of metal cation in T.S.
(zeff on valence shell of CMA / ion)
(2) (+ve) charge on metal cation
(3) Nature of surrounding ligands.
(4) Number of ligands (geometry of complex).
(5) Chelation effect
 –2.40' CFSE(max)
–2.00'
CFSE(max) CFSE(max)
–1.20 –1.60'

–1.20'

–0.80'
–0.40
–0.40'

d0 d1 d2 d3 d4 d5 d6 d7 d8 d9 d10 d0 d1 d2 d3 d4 d5 d6 d7 d8 d9 d10
CFSE in weak octahedron field CFSE in strong field ligand

Calculation of CFSE in tetrahedron field :

t2g t2g
+0.4't +0.4t
't t
Td. strong field ligand Td. weak field ligand
–0.6't –0.6t

eg eg
Filling of e–s in strong tetrahedron field. Filling of e–s in weak tetrahedron field.

CFSE (in strong Td. field) = –0.6 't × neg + 0.4 't × nt2g+ xP (additional pairing energy)

CFSE (in weak Td. field) = –0.6 t × neg + 0.4t × nt2g

CFSE(max)
–2.4t'
CFSE(max) CFSE(max)
–1.20
–1.8t'

–1.2t'
–0.6t
–0.6t'

d0 d1 d2 d3 d4 d5 d6 d7 d8 d9 d10 d0 d1 d2 d3 d4 d5 d6 d7 d8 d9 d10
i
CFSE in weak Td. field CFSE in strong Td. field

Factors affecting CFSE of complex compound :

CFSE also determines stability of complex compound therefore, it also named as crystal field stabilisation
energy. It depends upon following factors
(1) Position of metal cation in T.S.
(zeff on valence shell of CMA / ion)
(2) (+ve) charge on metal cation
(3) Nature of surrounding ligands.
(4) Number of ligands (geometry of complex).
(5) Chelation effect
(1) Type of metal cation : (zeff on valence shell of CMA / ion)
As higher the zeff on valence shell of metal cation, having same unit of +ve charge surrounded by same type
and same number of ligands, greater will be the CFSE.
2 10 Poor 2 6 10 Poor
s p6 d s p d
shielding shielding
18 18
3 6] ) 0
([CoF
3–
< ([RhF6] ) 0<
3–
([IrF6] ) 0 ( 0 <  0 <  0 )
3–

sp3d2 d2sp3 d2sp3

outer / octahedron inner / octahedron inner / octahedron
 = 24 BM  = 0 BM  = 0 BM
High spin Low spin Low spin
CFSE = –0.4 0 CFSE = –2.4 0' + 2P CFSE = –2.4 0" + 2P
(2) (+ve) charge on metal cation :
As higher the +ve charge on same type of metal cation, surrounded by same type and same number of
ligands, greater will be the CFSE. α Zeff oxidation state

E
2
 0 [Fe (NH3 )6 ] 2
< 0 [Fe (NH3 )6 ]3 
2
(0< 0)
396
sp3d2 (outer Orb. Complex) d2sp3 (inner Orb. Complex) (Limitation of CFT)
octahedron octahedron
MM = 24 BM (H.S.) M.M = 3 BM (L.S)
CFSE = 0.40 CFSE = –2.00 + 2P

(3) Nature of surrounding ligands :

As higher the electron donating tendency of surrounding ligands connected to the same type of metal cation,
having same unit of +ve charge, greater will be the CFSE.
• 0 [Fe 3 (CN)6 ]3  > 0 [Fe3 (NO2 )6 ]3  > 0 [Fe3 (NH3 )6 ]3 >  0 [Fe3 (H2 O)6 ]3 
d2sp3 (inner) d2sp3 (inner) d2sp3 (inner) sp3d2 (outer)
octahedron octahedron octahedron octahedron
= 3 BM(L.S.) = 3 BM(L.S) = 3 BM (L.S) = 35 BM (H.S.) 305
CFSE = –2.00 +2P CFSE = –2.00 + 2P CFSE = –2.00 + 2P CFSE = 0

• 0 [Co(en)3 ]3  > 0 [Co(ox)3 ]3  >  0 [Co(H2O)6 ]3  (Chelation Effect > Donation Effect)
d2sp3 (inner) d2sp3(inner) d2sp3 (inner) (limitation of C.F.T.)

Efffft
octahedron octahedron octahedron
 = 0 BM (LS)  = 0 BM (LS)  = 0 BM (L.S) 316
CFSE = –2.4 0 + 2P CFSE = –2.40 + 2P CFSE = –2.40 + 2P

Fei
I– < Br– < SCN– < Cl– < S2– < NO3– < F– < OH– < CH3COO– < C2O42– < H2O < NCS–...... (Spectrochemical series)

last outer orbital

complex [CoF6]3–

Note : Weak field ligands lying on the right side of F– ion in spectrochemical series unexpectedly form stable inner
orbital complex with Co3+ cation (limitation of C.F.T.).
(4) Number of surrounding ligands and geometry of complex :

4
sp > 0 > t ; sp = 1.30 ; t = 
9 0

Above relationships are valid when same type of metal cation with same unit of +ve charge is surrounded by
same type of ligands but they differ in number.

d8 d8
2
•  sp [Ni (NO2 )4 ] 2–
  0 [Ni2  (NO2 )6 ]4 – (sp = 1.30)
(sq.pl.) (Oct.)

dsp2 sp3d2
d8 d8
•  sp [Ni2  (NO2 )4 ]2–   0 [Ni2  (NH3 )6 ]4 – (sp  1.3 0)

traffff
(sq.pl.) (Oct.)

d6 d6
• 2
 Td [Fe Cl4 ] 2–
  0 [Fe Cl6 ] 2 4–  4 
  Td   0 
(Td) (Oct)  9 

d6 d6
•  Td [Fe2  Cl4 ]2–  0 [Fe2  (H2 O)6 ]2    Td  4  0 
(Td) (Oct)  9 

(5) Chelation effect :

As the number of stable rings (5 or 6 membered rings) increases in complex ion / compound, stability also
increase due to chelation effect.


Lt
[Ni2+(H2O)6]2+ (Less stable) + 3en 
 [Ni+2(en)3]2+ (More stable) + 6H2O

EE
G = H – TS H = –ve, S = +ve)
G = is more –ve at the given temperature (at R.T.)
It means stability increases due to chelation effect and equilibrium shift forward.

d3 d3 AG OH TOS
•
due to
3 3 3
 0 [Cr (en)3 ]   0 [Cr (NH3 )6 ]
chelation
•
d3 d3
'0 [Cr(en)3 ]3   [Cr(en)2 Cl2 ]3 

(3 rings) (2 rings)
gig I
d6 d6
'
• 0 [Co (EDTA)3 ]  0 [Co3  (NH3 )6 ]3 
3 –
(Chelation effect > Donation effect)

•  0 [Co3  (EDTA)]–   0 [Co3  (en)3 ]3  (Chelation effect > Donation effect)

(5 rings) (3 rings)

 0 [Co3  (ox)3 ]3–   0 [Co(H2O)6 ]3  (Chelation effect > Donation effect)

inner orbital complex inner orbital complex (Exceptions of CFT)
Note : Chelation effect is dominating over Donation effect (Chelation effect > Donation effect) except in case of
carbon as donor site of ligand.
Stability constant of complex ion :
Stability of complex ion can also be corelated with formation and dissociation constants as follows :
M4+ + 4L– [ML4]

Stepwise formation of complex :

k1
M4+ + L– ML3+

ML3+ + L– k2
ML22

k3
ML22 + L– ML3

k4
ML3 + L– [ML4]

k5

if
M4+ + 4L– [ML4] ;

kf = k1.k2.k3k4 ...........

 Log kf = log k1 + logk2 + logk3 + log k4 + ..........

1
kstability  kf  k
dissociation

Limitations of CFT :
3d5
(a) [Mn2 (NH ) ]2 Outer orbital complex , sp3d2 hybridization ,Octahedron ,MM = 35 BM (H.S)
3 6

3d6
(b) [Fe2  (NH ) ]2 Outer orbital complex , sp3d2 hybridization , Octahedron ,MM = 24 BM (H.S)
3 6

3d6
(c) [Co3  (H O) ]3  Inner orbital complex , d2sp3 hybridization, Octahedron ,MM = 0 BM (L.S)
2 6

(d) [Ni2 Cl2 (NH3 )2 ]0 Square planar ,dsp2 hybridization, MM = 0 BM (L.S)

308
Colour phenomenon of complex compounds
Complex compounds are coloured either by d-d transition or by charge transfer phenomenon.

(1) d-d transition : Unpaired electron of metal cation is involved in (d-d) transition, if it is lying in visible region
then complex compound is coloured.

[Ti3  (H2O)6 ]3  : Complex ion is purple in colour due to d-d transition.

Blue Green
eg
hc Violet
d-d E = h = Yellow

I
 Indigo
Splitting in transition
oct-field
Red Orange
It
t2g

1
CFSE  frequency of absorbed light 
wavelength of absorbed light
Note :
(1) Complex compound in which metal cation is having d0 or d10 configuration are colorless due to no scope of
d-d transition.

(2) If any octahedron or tetrahedron complex is coloured, then colour is either due to d-d transition or due to
charge transfer phenomenon.

(3) If any square planar complex is coloured, then colour is only due to charge transfer phenomenon.

(4) Colour intensity due to charge transfer phenomenon is more than d-d transition.

(5) In d-d transition unpaired electron is involved whereas in charge transfer shared electron is involved in transition.

(2) Charge transfer spectrum (CT phenomenon) :

Momentary change in oxidation state of the central metal atom (CMA) / ion or ion due to shared electron
transition is called charge transfer spectrum. e.g. Charge Transfer Spectrum in permangnate (MnO4–) ion.

O2–
–
O

+7 +6
Mn+7 After replacement of 
-bond
3 Mn

O2– O2– O– O–
2– –
O O
Ligands are in Pink/purple colour is due to momentary
non-axial direction change in O.S. of Mn cation

• C.T. spectrum may occurs by following three ways :

(1) Ligand to metal (L M) charge transfer phenomenon.

3d0
Mn O –4 (Pink/purple)
7

I
3d1
Mn6 O 2– (Green)
4

3d0
Cr 6 O 2– (Yellow) Specific colour of complex compounds is due to (ligand  metal) charge
4
1
3d
Cr26 O72– (Orange) transfer phenomenon

a
a
5
VO3–
4

[Fe(H
(Blue)

2O)5(NO)]SO4
CITIES
main
retail
(Brown ring complex)

(2) Metal to ligand (ML) charge transfer phenomenon.

M(CO)x (Coloured Compounds)
K4[Fe(CN)6] (Pale yellow)
K3 [Fe(CN)6] (Yellow) Specific colour of complex is due to (metal  ligand) CT spectrum
Na4 [Fe(CN)5(NOS)] (Purple) i
Occurs through synergic bonding.
 (3) Metal to metal (MM) charge transfer phenomenon.
3+ 3+
Fe [Fe (CN)6]
Reddish Brown solution
Ferri ferri cyanide

Cu2[Fe2+(CN)6]  (Chocolate Brown ppt)

Cu3[Fe(CN)6]2  (Green ppt)

Redox

3+ 2+
Fe4 [Fe (CN)6]3  Prussian Blue
Ferri ferro cyanide
Redox
I
2+ 3+
Fe3 [Fe (CN)6]2 
8 Ferro ferro cyanide
Turnbull’s Blue
3
Both Fe34 [Fe(CN)6]3 and Fe23 [Fe(CN)6]2 exist in solution simultaneously due to partial redox between Fe3+
and Fe2+ cations and can also be represented by common formula as follows.
3+ 2+
Fe [Fe (CN)6]
(Prussian blue)
Common –
Fe[Fe(CN)6]
formula
2+ 3+
Fe [Fe (CN)6]
(Turnbull's blue)

TEXT QUESTIONS
1. Predict the magnetic moment and geometry of following complex and also explain their colour phenomenon.
(a) CrO2–
4
(Chromate ion)

(b) MnO 2–
4
(Manganate ion)
3d
(c) Cr2 O72 – (Dichromate ion)
(d) [Fe(H2O)5(NO)]SO4 (Brown ring complex) 3d
(e) Na2[Fe(CN)5NO] (Sodium Nirtroprusside)
Sol.
Gtb (a) 6 2– (Chromate ion)  d3s Hybridization  Td Geometry , MM = 0 BM (Diamagnetic)
CrO 4

(b) MnO2–
4
(Manganate ion)  d3s Hybridization  Td Geometry , MM = 3 BM (Paramagnetic)

(c) Cr2O72– (Dichromate ion)  d3s Hybridization  Td Geometry , MM = 0 BM (Diamagnetic)

(d) [Fe1+(H2O)5(NO1+)]SO4  sp3d2 Hybridization Oct Geometry , MM = 15 BM (Paramagnetic)

f (e) Na2 [Fe2  (CN)5 NO1 ] 2  d2sp3 Hybridization  Oct Geometry , MM = 0 BM (diamagnetic)

ten 3d

dxy dyz dzx

4s 4p

= 0 BM
6+ 2–
(a) Cr O4 Td geometry
3
Yellow colour is d s hybridization
due to ligand to metal
charge transfer
 3d 4s 4p

dxy dyz dzx

= 0 BM
7+ –
(b) Mn O4 Td geometry
3
Pink/purple colour d s hybridization
is due to ligand to metal
charge transfer

3d 4s 4p

dxy dyz dzx

= 0 BM
2–
(c) Cr2O7 Td geometry
3
Orange colour d s hybridization
is due to ligand to metal
charge transfer

Note : Chromate & Dichromate ions are in equilibrium with each other. Dichromate exists in acidic medium
while Chromate exists in basic medium. Whenever CrO42– / H+ (acidifed Chromate) is written, it
means it is Cr2O72– (Dichromate) so colour will be orange (not yellow).

O O O
pH > 7
Cr Cr Cr
–
O O O O O
–
pH < 7 –
O O O
–

Dichromate ion exists Chromate ion exists

in acidic medium in basic medium

(d) [Fe(H2O)5(NO)]SO4 (Brown ring complex)

3 2
sp d hybridization

0
Energy 4p
gap
6+1
d
1+ 1+
[Fe (H2O)5NO ]SO4 Outer orbital complex
Brown colour  = 15 BM (L.S)
due to (L  M)C.T. phen. CFSE = 0.8 0 + P

(e) Na2[Fe2
1+(CN) NO1+] Sodium nitroprusside
5

4s 4p
3d

d2sp3 hybridization
inner orbital complex
Colourless low spin complex MM=0
C–T phen does not octahedron geometry
lie in visible region

Splitting in strong
octahedron field
 mandarins
mÉ
2. Three complex ion [M(en)3]2+, [M(H2O)6]2+, [MBr6]4– are red, blue and green coloured in aqueous solution
match these ions with their appropriate colour.
Sol. [M2+(en)3]2+ > [M2+(H2O)6]2+ > 0[M2+(Br)6]4–
emitlight
1
CFSE  frequency of absorbed light 
Wavelength of absorbed light Red Blue
Emitted colours Red Blue Green

EE
Absorbed colour Green Orange Red

UV Visible IR
region region region

[M(en)3]2+  Red
[M(H2O)6]2+  Blue
[M(Br)6]2+  Green
 (3) Metal to metal (MM) charge transfer phenomenon.
3+ 3+
Fe [Fe (CN)6]
Reddish Brown solution
Ferri ferri cyanide

I
Cu2[Fe2+(CN)6]  (Chocolate Brown ppt)

Cu3[Fe(CN)6]2  (Green ppt)

Redox

3+ 2+
Fe4 [Fe (CN)6]3  Prussian Blue 2
2 3
Ferri ferro cyanide
Redox
I
2+ 3+
Fe3 [Fe (CN)6]2 
8 Ferro ferro cyanide
Turnbull’s Blue
e3
Both Fe34 [Fe(CN)6]3 and Fe23 [Fe(CN)6]2 exist in solution simultaneously due to partial redox between Fe3+
and Fe2+ cations and can also be represented by common formula as follows.
3+ 2+
Fe [Fe (CN)6]
(Prussian blue)
Common –
Fe[Fe(CN)6]
formula
2+ 3+
Fe [Fe (CN)6]
(Turnbull's blue)

TEXT QUESTIONS
1. Predict the magnetic moment and geometry of following complex and also explain their colour phenomenon.
(a) CrO2–
4
(Chromate ion)

(b) MnO 2–
4
(Manganate ion)
3d
(c) Cr2 O72 – (Dichromate ion)
(d) [Fe(H2O)5(NO)]SO4 (Brown ring complex) 3d
(e) Na2[Fe(CN)5NO] (Sodium Nirtroprusside)
Sol.
Gtb (a) 6 2– (Chromate ion)  d3s Hybridization  Td Geometry , MM = 0 BM (Diamagnetic)
CrO 4

(b) MnO2–
4
(Manganate ion)  d3s Hybridization  Td Geometry , MM = 3 BM (Paramagnetic)

(c) Cr2O72– (Dichromate ion)  d3s Hybridization  Td Geometry , MM = 0 BM (Diamagnetic)

(d) [Fe1+(H2O)5(NO1+)]SO4  sp3d2 Hybridization Oct Geometry , MM = 15 BM (Paramagnetic)

f (e) Na2 [Fe2  (CN)5 NO1 ] 2  d2sp3 Hybridization  Oct Geometry , MM = 0 BM (diamagnetic)

ten tag
3d

dxy dyz dzx

4s 4p

= 0 BM
6+ 2–
(a) Cr O4 Td geometry
3
Yellow colour is d s hybridization
due to ligand to metal
charge transfer

eg
 3d 4s 4p

dxy dyz dzx

= 0 BM
7+ –
(b) Mn O4 Td geometry
3
Pink/purple colour d s hybridization
is due to ligand to metal
charge transfer

3d 4s 4p

dxy dyz dzx

= 0 BM
2–
(c) Cr2O7 Td geometry
3
Orange colour d s hybridization
is due to ligand to metal
charge transfer

Note : Chromate & Dichromate ions are in equilibrium with each other. Dichromate exists in acidic medium
while Chromate exists in basic medium. Whenever CrO42– / H+ (acidifed Chromate) is written, it
means it is Cr2O72– (Dichromate) so colour will be orange (not yellow).

O O O
pH > 7
Cr Cr Cr
–
O O O O O
–
pH < 7 –
O O O
–

Dichromate ion exists Chromate ion exists

in acidic medium in basic medium

(d) [Fe(H2O)5(NO)]SO4 (Brown ring complex)

3 2
sp d hybridization

0
Energy 4p
gap
6+1
d
1+ 1+
[Fe (H2O)5NO ]SO4 Outer orbital complex
Brown colour  = 15 BM (L.S)
due to (L  M)C.T. phen. CFSE = 0.8 0 + P

Na2[Fe2
2
(e) 1+(CN) NO1+] Sodium nitroprusside
5

4s 4p
396 3d

d2sp3 hybridization
inner orbital complex
Colourless low spin complex MM=0
C–T phen does not octahedron geometry
lie in visible region

Splitting in strong
octahedron field
 mandarins
mÉ
2. Three complex ion [M(en)3]2+, [M(H2O)6]2+, [MBr6]4– are red, blue and green coloured in aqueous solution
match these ions with their appropriate colour.

emitlight
TT
Sol. [M2+(en)3]2+ > [M2+(H2O)6]2+ > 0[M2+(Br)6]4–

CECFSE  frequency of absorbed light  Wavelength of1absorbed light Red Blue

Emitted colours Red Blue
75 1Green 0

EE
Absorbed colour Green Orange Red

am
colony
IEEE UV
region
Visible
region
E IR
region
tm

[M(en)3]2+  Red
[M(H2O)6]2+  Blue
[M(Br)6]2+  Green

CFSE Dolmax Energy absorbmax dabsorb min

INORGANIC CHEMISTRY

NOTES

COORDINATION
COMPOUNDS
PART 6
 mandarins
• Isomerism in complex compounds : mÉ
When complex compounds have same molecular formula but have different structural or spacial arrangements
of ligands around central metal atom or ion, are called isomers and phenomenon is named as isomerism.
Complex compound exhibit mainly two types of isomerism.
(1) Structural isomerism (2) Space or stereoisomerism
Isomerism

Structural isomerism Space / Stereo isomerism

Ionisation isomerism Geometrical isomerism (cis-trans isomerism)
Hydrate(solvate) isomerism Optical isomerism
Linkage isomerism
Coordination isomerism
Coordination position isomerism
ionisation
1. Ionisation isomerism : sphere from
It occurs in those complex compounds which give different types of simple ions in aqueous solution on
ionisation are called ionisation isomers and phenomenon is named as ionisation isomerism.
+3 0 –2
[Cr(NH3)5 SO4] Br Water
+ – + –
Ex. [Cr(NH3)5 SO4] + Br (Br– gives pale yellow ppt of AgBr on adding AgNO3 solution)
+3 0 – +2
[Cr(NH 3)5 Br] SO 4 Water [Cr(NH3)5 Br] + SO4 ( SO2–
2– 2–
+
4
gives white ppt of BaSO4 on adding BaCl2 solution)
The above pair is an example of ionisation isomerism.

[PtCl2(NH3)4]Br2

[PtBrCl(NH3)4]BrCl Possible ionisation isomers of given complex = 2

Total ionisation isomers = 3
[PtBr2(NH3)]Cl2

3+ + –
[Co (NO2)(SCN)(NH3)4] Cl
3+ + –
[Co Cl(SCN)(NH3)4] NO2 Possible ionisation isomers of given complex = 2
3+ + – Total ionisation isomers = 3
[Co Cl(NO2)(NH3)4] SCN
i
Note : Oxidation state and coordination number of central metal atom (CMA) or ion must remain constant
in all possible isomers.

2. Hydrate (solvate) isomerism :

It occurs in those complex compounds in which few coordinated water molecules become water of hydration
in ionisation sphere are called hydrate isomers and phenomenon is named as hydrate isomerism.

Ex. [Cr(H2O)6]Cl3
[Cr(H2O)5Cl]Cl2.H2O Possible hydrate isomers of given compound = 2
[CrCl2(H2O)4]Cl.2H2O Total hydrate isomers = 3
Water of crystalisation occurs in ionic solid in presence of Cation and Anion (not in neutral complex compound).

[Co2 NO2 )(H2 O)(NH3 )4 ]Cl  No hydrate isomers and one ionisation isomer [CoCl(H2O)(NH3)4]NO2

[Co3+(NO2)(H2O)(NH3)4]Cl2  Only one hydrate isomer and one ionisation isomers
[Co(Cl)(H2O)(NH3)4]Cl.NO2 , [Co(NO2)(Cl)(NH3)4]Cl.H2O , [CoCl2(NH3)4]NO2.H2O (not defined)

II
(I.I.) (H.I.) (I.I. of H.I. / H.I. of II )

E IF TT
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 8 No 102 emo
3. Linkage isomerism :
changdonor.com
It occurs in those complexes which contain at least one ambidentate ligand. That can coordinate with CMA/
ion through either of the two donor sites are called linkage isomers.

Ex. [Co(NO2)(H2O)(NH3)4]Cl2  [Co(ONO)(H2O)(NH3)4]Cl2 (Only one Linkage isomers)

• [Cr(NO2)(SCN)(en)2]CN  [Cr(ONO)(SCN)(en)2]CN
I
say
l [Cr(NO2)(NCS)(en)2]CN

Possible linkage isomers = 3 ,

[Cr(ONO)(NCS)(en)2]CN
Total linkage isomers = 4
Ecs
• [Cr3+(SCN)(NH3)5]2+ [Zn2+(CN)4]2–  4 linkage isomers

t.IE
[Cr3+(NCS–)(NH3)5]2+[Zn2+(CN)4]2–  4 linkage isomers
Possible linkage isomers = 9 , Total linkage isomers = 10
innar
4. Coordination isomerism : isomer I
It occurs in those complex compounds is which both cation and anion are complex. In such cases, ligands
are interchanged between the coordination spheres and they are called coordination isomers.
2 11 1 2
Ex. [Pt2+(NH3)4]2+ [Cu2+(Cl)4]2–  [PtCl(NH)3]1+ [CuCl3(NH3)]1–
[CuCl(NH3)3]+ [PtCl3(NH3)]–
[Cu(NH3)4]2+ [PtCl4]2–
Possible coordination isomers = 3 ; Total coordination isomers = 4
3 2 1
• 3+ 3+ 3+
[Fe (NH3)6] [Co (NO2)6] 3–  [Fe (C.N.)6] 2+/1+ [Co (C.N.)6] 2–/1–

[Co (C. N.)6 ]1+/2+/3+ [Fe (C.N.)6]1–/2–/3– 1 2 3

Possible coordination isomers = 5 Total coordination isomers = 6

3 changes NH3  SCN–

3+
–1
2+ 2+ 2–
1  1 
• [Cr (NH3)5 (SCN)] [Zn Cl4] 2  1 
1 change 3  1 

Possible coordination isomers = 3 (w.r.t. NH3) + 1 (w.r.t. SCN–) + 2 (w.r.t. NH3 & SCN–) = 6

(5) Coordination positonal isomerism :

It occurs in polynuclear or bridging complex compounds in which terminal ligands are interchanged between
the metal nuclei.
This change is
not defined
OH 4+ OH 4+
Ex. (NH3)4Cr  (H2O)(NH3)3Cr
Cr(NH3)2(H2O)2 Cr(NH3)2(H2O)
OH OH
(Only 1 coordination position isomer)
0
0 Cl Cl PPh3
Cl
+2 +2
• Cl2Pd Pd(PPh3)2  Pd Pd
Cl Cl Cl PPh3
(Only 2 coordination position isomers)

Ira at
Polymerisation isomerism (not true isomers) :
It is not true isomerism and occurs in those complex compounds which have their same empirical formula
but have different molecular formula.

Ex. [Pt2+Cl2(NH3)2]n = 1, 2, 3 (Empirical formula of complex must be neutral species)

n=1 [Pt2+Cl(NH3)2]
n = 2 (1 + 1) [Pt2+(NH3)4] [Pt2+Cl4]  1
more
  [Pt2+(NH3)3Cl]+[Pt2+Cl3(NH3)]
Coordination isomer
1 more
n = 3 (1 + 2) [Pt2+(NH3)4]2+ [Pt2+Cl 3(NH3)]2       [Pt2+Cl(NH3)3 ]2 [PtCl4]
so Coordination isomer
All above complex compounds are polymerisation isomers

QUESTIONS FOR PRACTICE–7

Single Choice Question :
1. The two compounds pentaamminesulphatocobalt(III) bromide and
pentaamminesulphatocobalt(III) chloride represent
(A) Linkage isomerism (B) Ionization isomerism
(C) Coordination isomerism (D) No isomerism

2. Which one of the following is an example of coordination isomerism?

(A) [Co(NH3)5Br]SO4 and [Co(NH3)5SO4]Br (B) [Co(NH3)5NO2]Cl2 and [Co(NH3)5ONO]Cl2
(C) [Cr(H2O)6]Cl3 and [Cr(H2O)5Cl]Cl2 ·H2O (D) [Cr(NH3)6][Co(CN)6] and [Co(NH3)6][Cr(CN)6]
3. [Cr(NH3)5Br]Cl and [Cr(NH3)5Cl]Br can be distinguished by/and isomerism shown is:
(A) BaCl2, ionisation (B) AgNO3, ionisation
(C) AgNO3, coordinate (D) BaCl2, linkage

4. The total possible co-ordination isomers for the following compounds respectively are
[Co(en)3] [Cr(C2O4)3] [Cu(NH3)4] [CuCl4] [Ni(en)3] [Co(NO2)6]
(A) 4, 4, 4 (B) 2, 2, 2 (C) 2, 2, 4 (D) 4, 2, 3

Comprehension-1 (5 to 7)
Complex compounds which have same molecular formula but have different structural arrangements of ligands
around central metal atom or ion are called structural isomers and phenomenon is named as structural
isomerism.
5. Which of the following compounds is/are polymerisation isomer of [Fe(NO2)3(NH3)3].
(I) [Fe(NO2)(NH3)5] [Fe(NO2)5(NH3)] (II) [Fe(NO2)2(NH3)4]2 [Fe(NO2)5(NH3)]
(III) [Fe(NO2)(NH3)5] [Fe(NO2)4(NH3)2]2 (IV) [Fe(NO2)2(NH3)4] [Fe(NO2)4(NH3)2]
Choose the correct code :
(A) II, III (B) II, III, IV (C) I, IV (D) I, II, III, IV

6.
__
How many more coordination isomers are possible of the following complex compound.
[PtCl2 (NH3)4] [Pt (SCN)4]
(A) 5 (B) 6 (C) 8 (D) 9
7. Select incorrect match
(A) [Co(NO2)(H2O)(en)2)]Cl2, [CoCl(NO2)(en)2] Cl . H2O – Hydrate isomerism

(B) [Cu(NH3)4][PtCl4], [CuCl2(NH3)2] [PtCl2(NH3)2] – Coordination isomerism

(C) [Ni(CN)(H2O)(NH3)4]Cl, [NiCl(H2O)(NH3)4]CN – Ionization isomerism

(D) [Cr(NCS)(NH3)5] [ZnCl4], [Cr(SCN)(NH3)5] [ZnCl4] – Linkage isomerism

Subjective :
8. Find out number of more possible coordiantion isomers of complex [PtCl3(NH3)3] [Au(NO2)4].
 mandarins
• Isomerism in complex compounds : mÉ
When complex compounds have same molecular formula but have different structural or spacial arrangements
of ligands around central metal atom or ion, are called isomers and phenomenon is named as isomerism.
Complex compound exhibit mainly two types of isomerism.
(1) Structural isomerism (2) Space or stereoisomerism
Isomerism

Structural isomerism Space / Stereo isomerism

Ionisation isomerism Geometrical isomerism (cis-trans isomerism)
Hydrate(solvate) isomerism Optical isomerism
Linkage isomerism
Coordination isomerism
Coordination position isomerism
ionisation
1. Ionisation isomerism : sphere from
It occurs in those complex compounds which give different types of simple ions in aqueous solution on
ionisation are called ionisation isomers and phenomenon is named as ionisation isomerism.
+3 0 –2
[Cr(NH3)5 SO4] Br Water
+ – + –
Ex. [Cr(NH3)5 SO4] + Br (Br– gives pale yellow ppt of AgBr on adding AgNO3 solution)
+3 0 – +2
[Cr(NH 3)5 Br] SO 4 Water [Cr(NH3)5 Br] + SO4 ( SO2–
2– 2–
+
4
gives white ppt of BaSO4 on adding BaCl2 solution)
The above pair is an example of ionisation isomerism.

[PtCl2(NH3)4]Br2

[PtBrCl(NH3)4]BrCl Possible ionisation isomers of given complex = 2

Total ionisation isomers = 3
[PtBr2(NH3)]Cl2

3+ + –
[Co (NO2)(SCN)(NH3)4] Cl
3+ + –
[Co Cl(SCN)(NH3)4] NO2 Possible ionisation isomers of given complex = 2
3+ + – Total ionisation isomers = 3
[Co Cl(NO2)(NH3)4] SCN
i
Note : Oxidation state and coordination number of central metal atom (CMA) or ion must remain constant
in all possible isomers.

2. Hydrate (solvate) isomerism :

It occurs in those complex compounds in which few coordinated water molecules become water of hydration
in ionisation sphere are called hydrate isomers and phenomenon is named as hydrate isomerism.

Ex. [Cr(H2O)6]Cl3
[Cr(H2O)5Cl]Cl2.H2O Possible hydrate isomers of given compound = 2
[CrCl2(H2O)4]Cl.2H2O Total hydrate isomers = 3
Water of crystalisation occurs in ionic solid in presence of Cation and Anion (not in neutral complex compound).

[Co2 NO2 )(H2 O)(NH3 )4 ]Cl  No hydrate isomers and one ionisation isomer [CoCl(H2O)(NH3)4]NO2

[Co3+(NO2)(H2O)(NH3)4]Cl2  Only one hydrate isomer and one ionisation isomers
[Co(Cl)(H2O)(NH3)4]Cl.NO2 , [Co(NO2)(Cl)(NH3)4]Cl.H2O , [CoCl2(NH3)4]NO2.H2O (not defined)

II
(I.I.) (H.I.) (I.I. of H.I. / H.I. of II )

E IF TT
Polymerisation isomerism (not true isomers) :
It is not true isomerism and occurs in those complex compounds which have their same empirical formula
but have different molecular formula.

Ex. [Pt2+Cl2(NH3)2]n = 1, 2, 3 (Empirical formula of complex must be neutral species)

n=1 [Pt2+Cl(NH3)2]
n = 2 (1 + 1) [Pt2+(NH3)4] [Pt2+Cl4]  1
more
  [Pt2+(NH3)3Cl]+[Pt2+Cl3(NH3)]
Coordination isomer
1 more
n = 3 (1 + 2) [Pt2+(NH3)4]2+ [Pt2+Cl 3(NH3)]2       [Pt2+Cl(NH3)3 ]2 [PtCl4]
so Coordination isomer
All above complex compounds are polymerisation isomers

QUESTIONS FOR PRACTICE–7

Single Choice Question :
1. The two compounds pentaamminesulphatocobalt(III) bromide and
pentaamminesulphatocobalt(III) chloride represent
(A) Linkage isomerism (B) Ionization isomerism
(C) Coordination isomerism (D) No isomerism

2. Which one of the following is an example of coordination isomerism?

(A) [Co(NH3)5Br]SO4 and [Co(NH3)5SO4]Br (B) [Co(NH3)5NO2]Cl2 and [Co(NH3)5ONO]Cl2
(C) [Cr(H2O)6]Cl3 and [Cr(H2O)5Cl]Cl2 ·H2O (D) [Cr(NH3)6][Co(CN)6] and [Co(NH3)6][Cr(CN)6]
3. [Cr(NH3)5Br]Cl and [Cr(NH3)5Cl]Br can be distinguished by/and isomerism shown is:
(A) BaCl2, ionisation (B) AgNO3, ionisation
(C) AgNO3, coordinate (D) BaCl2, linkage

4. The total possible co-ordination isomers for the following compounds respectively are
[Co(en)3] [Cr(C2O4)3] [Cu(NH3)4] [CuCl4] [Ni(en)3] [Co(NO2)6]
(A) 4, 4, 4 (B) 2, 2, 2 (C) 2, 2, 4 (D) 4, 2, 3

Comprehension-1 (5 to 7)
Complex compounds which have same molecular formula but have different structural arrangements of ligands
around central metal atom or ion are called structural isomers and phenomenon is named as structural
isomerism.
5. Which of the following compounds is/are polymerisation isomer of [Fe(NO2)3(NH3)3].
(I) [Fe(NO2)(NH3)5] [Fe(NO2)5(NH3)] (II) [Fe(NO2)2(NH3)4]2 [Fe(NO2)5(NH3)]
(III) [Fe(NO2)(NH3)5] [Fe(NO2)4(NH3)2]2 (IV) [Fe(NO2)2(NH3)4] [Fe(NO2)4(NH3)2]
Choose the correct code :
(A) II, III (B) II, III, IV (C) I, IV (D) I, II, III, IV

6.
__
How many more coordination isomers are possible of the following complex compound.
[PtCl2 (NH3)4] [Pt (SCN)4]
(A) 5 (B) 6 (C) 8 (D) 9
7. Select incorrect match
(A) [Co(NO2)(H2O)(en)2)]Cl2, [CoCl(NO2)(en)2] Cl . H2O – Hydrate isomerism

(B) [Cu(NH3)4][PtCl4], [CuCl2(NH3)2] [PtCl2(NH3)2] – Coordination isomerism

(C) [Ni(CN)(H2O)(NH3)4]Cl, [NiCl(H2O)(NH3)4]CN – Ionization isomerism

(D) [Cr(NCS)(NH3)5] [ZnCl4], [Cr(SCN)(NH3)5] [ZnCl4] – Linkage isomerism

Subjective :
8. Find out number of more possible coordiantion isomers of complex [PtCl3(NH3)3] [Au(NO2)4].
Pt as Nhs Añ Now

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Fantine Efurans
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as well as
unsymmel
then known as enantiomers
they are

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which is capable of

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compd is opticellytime
present then
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 Space or Stereo isomerism

Geometrical isomerism Optical isomerism

(GI) (OI)

When complex compound have same molecular formula but have different spacial arrangement of ligands
around CMA/ion in 3-D space are called stereo/space isomers and phenomenon is named as space/stereo
isomerism.
GI is shown by that compound in which every position of geometry must have its atleast one cis
position and only one trans position.
OI is shown by that compound having no POS and COS.

GI and OI in complex compounds with CN = 4

1. Possible geometry of complex compound with coordination number 4 is tetrahedron and square planar.
Tetrahedron geometry never exhibit GI because in this geometry, all positions are adjacent to one another.
However GI is very common in square planar complexes.

2. All non-chelating square planar complexes are mostly optically inactive due to having POS in molecular
plane. However chelating complex may be optically active when linkage of chelating ligand is having a chiral
centre.

3. Tetrahedron geometry is optically active when it is having chiral centre (all four donor sites of ligands are
different)

4. Complex compounds in which Be2+ or Zn2+ is surrounded by four any type of ligands always form Tetrahedral
geometry.
5. Complex compounds in which Pd2+ or Pt2+ is surrounded by four any type of ligands always form square
planar geometry.
6. Adjacent donor site of bidentate and multidentate ligands always occupy adjacent position of geometry.
They never occupy anti position of geometry.

GI is square planar complexes :

In square planar complex cis and trans form is defined w.r.t. group having only two ligands.
[Ma4]n± [Mab3]n± [M(AA)2]n± [M(AA)b2]n± [M(AA)bc]n± [M(AB)c2]n± [M(AB)(CC)]n± type of square planar
ligands do not exhibit GI (where a, b, c  monodentate ligands, AA  Symmetrical bidentate ligand,
AB  Unsymmetrical bidentate ligand)
GI is shown in :
• [Ma2b2]n± where a, b are monodentate ligands.
n± n±
a b a b

M M
a b b a
Cis Trans
2 2
e.g. [PtCl2(NH3)2]0, [PtCl2(py)2]0

0 0
Cl NH3 Cl NH3

Pt Pt
Cl NH3 NH3 Cl
Cis-platin Trans-platin
(used as an anti-cancer drug)

• [Ma2bc]n± where a, b are monodentate ligands

e.g. [Pt2+BrCl(NH3)2]0, [Pd2+BrCl(py)2]0

a b a b

M M
a c c a
Cis form Trans form
• [Mabcd]n± where a, b, c are monodentate ligands.
n± n± n±
a c a b a b

M M M
GI
d b d c c d
I form II form III form
Three GI are possible but they are not defined in terms of cis and trans forms.

• [M(AB)2]n± where (AB) is unsymmetrical bidentate ligand.

e.g. [Pt(gly)2]0
n± n± O
A A A B
CH2 – C
M M H2N O
B B B A
Cis Trans

H2 H2 H2 O
H2C–N N–CH2 H2C–N O–C

Pt Pt
C O O C C O N C
O Cis form O O
Trans form
H2 H2 ME'd
• [M(AB)cd]n±

I'm 9
two GI are possible but cis & trans forms are not defined.
• [M(AB)(CD)]n±

__
Ex. Predict possible number of GI and OI of given complexes.
(a)42
[Pt(NH2CHMeCOO)2]0 (b) [PdCl2(PPh3)]2
2
sq.planen
Me
H
C–N
2 H2
N–C
H O
C–O
H2
N–C
H

MDFE.ro
H Me Me
Pt Me Pt

c.o. c
C O O C C N O C
(a)
O O H2 O
I
Iafas
H
Cis form Trans form
H optically active optically inactive due to COS

Lo
POS
Me H2
C–N
H2
N–C
Me
o O
C–O
H2
N–C
Me
it
I H H H

me I
C O
Pt
O C
Me
C N
H2
Pt
O C
c
O O H O
Cis form Trans form
optically inactive optically active
Cis form = 2 Trans form = 2

Here [Pt(NH2CHMe(COO)2] , GI = 4(2 cis + 2 trans), OI = 6(4 + 2) , Total space isomers = 6

(b) [Pd2+Cl2(PPh3)]2
0
Cl Cl PPh3

Pd Pd
(No GI)
Cl Cl PPh3

I 0
PPh3 Cl Cl

Cl
Pd
Cl
Pd
PPh3
Trans form
i
1 0
PPh3 Cl PPh3
Pd Pd
Cis form
Cl Cl Cl
i
GI = 2(1 + 1) OI = 0 Total space isomers = 2

Optical Isomerism in tetrahedral complexes :

Tetrahedral complex is optically active when it is having a chiral centre.
[Ma4]n±, [Ma3b]n± , [Ma2b2]n± , [Ma2bc]n± , [M(AA)2]n±, [M(AA)b2]n±, [M(AA)bc]n±, [M(AB)c2]n±,
[M(AB)(CC)]n± such type of tetrahedral complexes are optically inactive due to the presence of POS.
 died
[M(abcd)]n± types of complex is optically active.

a n± a
n±

b M d M b
PII
d
c c
d-form Mirror -form
e.g. 22
[ZnBrCl(NH )(py)]0  optically active :
3

Br 0 Br 0

Cl Zn py py Zn Cl LOI
NH3 NH3
d-form -form
• [M(AB)2]n±  (optically active) where AB = unsymmetrical bidentate ligand.

A n± A n± O
H2C–C
B M B B M B
H2N O¯
A A M
d-form -form Glycinate ion
(Unsym. bidentate ligand)

É
e.g. [Be(gly)2]

0 0

É
N N

si
O Be O O Be O

N N
d-form -form

Text Question :Comment on optical activity phenomenon.

(a) [Zn(acac)2]0  [M(AA)2]  Optically inactive
je
(b)
I
[Zn(bcac)2]0  [M(AB)2]  Optically active BE
I
in

Itunsyme
(c) [Zn(dien)Br]+  [M(AAA)b]  Optically inactive M
Geometrical and Optical Isomerism in octahedral complexes
(1) In oct. geometry cis & trans form is defined w.r.t. group having either two ligands are three ligands.
(2) In oct. geometry, when two same ligands are present at any anti position of geometry, then it is
optically inactive due to having POS of remaning four ligands.

[Ma6]n± , [Ma5b]n± , [M(AA)b4]n± such type of octahedral complexes do not show GI and OI.

• [Ma4b2]n± (where a, b are monodentate ligands)

b b planardo s
b a a a
M M
a a a a
a b
(cis form)
(Trans form)

i
Optically inactive Optically inactive
due to POS
due to POS
 died
[M(abcd)]n± types of complex is optically active.

a n± a
n±

b M d M b
PII
d
c c
d-form Mirror -form
e.g. 22
[ZnBrCl(NH )(py)]0  optically active :
3

Br 0 Br 0

Cl Zn py py Zn Cl LOI
NH3 NH3
d-form -form
• [M(AB)2]n±  (optically active) where AB = unsymmetrical bidentate ligand.

A n± A n± O
H2C–C
B M B B M B
H2N O¯
A A M
d-form -form Glycinate ion
(Unsym. bidentate ligand)
e.g. [Be(gly)2]

0 0

É
N N

si
O Be O O Be O

N N
d-form -form

Text Question :Comment on optical activity phenomenon.

(a) [Zn(acac)2]0  [M(AA)2]  Optically inactive
je
(b)
I
[Zn(bcac)2]0  [M(AB)2]  Optically active BE
(c)
I
[Zn(dien)Br]+  [M(AAA)b]  Optically inactive

Geometrical and Optical Isomerism in octahedral complexes T.tt

M
unsyme
m

or
(1) In oct. geometry cis & trans form is defined w.r.t. group having either two ligands are three ligands.
(2) In oct. geometry, when two same ligands are present at any anti position of geometry, then it is
optically inactive due to having POS of remaning four ligands.

[Ma6]n± , [Ma5b]n± , [M(AA)b4]n± such type of octahedral complexes do not show GI and OI.

• [Ma4b2]n± (where a, b are monodentate ligands)

b b planardo s
b a a a
M M
a a a a
a b
(cis form)
(Trans form)

i
Optically inactive Optically inactive
due to POS
due to POS 11,2 11,3 1,4 1,5
12,3 215 314 4,5
12,61 3,6 4161 1516
e.g. [CrCl2(NH3)4]+, [Co(NO2)2(NH3)4]+
+ +
Cl Cl
Cl NH3 NH3 NH3
Cr Cr G I 2
NH3 NH3 NH3 NH3
NH3 Cl
0 I 2
(cis form) (trans form)

• [Ma4bc]n± type of complex

b n± b n±
a a a a
M M
a c a a
a c
(cis form)
(trans form)
Optically inactive Optically inactive
due to POS
due to POS

• [Ma3b3]n± type of complex

a n± a n±
b a b b
M M
b a a b
b a
(cis form) (trans form)
(Facial form/fac form)
(Meridional/mer form)

Cl
if
Cl
Cl
n±
NH3
Cl
NH3
n±

NH3
Cr

NH3
NH3 NH3 ICl Cl
Cr

trans
cis
(fac form) (mer form)
(optically inactive)
(optically inactive)

M9zb3 111 I1
ME
iata path 15T
Ibt b
at a a TC
c

FS Atb at
39.1 latb
Ma2b
b t
cat
bts btc
1959
19T Cbt b Cate
at b CTC
19T b

This

0 Isomer 6

total stereoiso 6

enan 1
pair

M93b
a e at b let d
a
atal fat i 1st d o.tn e
bt e
a a Td
19T

cnn.in
M92b
b Ctd
a a got
btc bid
fatal
bib fat d
late
Cathy Cats
Itd fÉ on

at C b Tdl
19Th
b at 4 btc
19T

man

Cfative 11 Total 9 I 6

Total 0 I 8
2
enpair
Total S I 8
 m
o
ab ab
ad ie if
af dt de

ac ac ac
121

it
ad ad ad
31
b e be b5
e f f ce

ae ae ae
141
bt
If I ce

af af
157 at
be bd
ma

otradI
strand
ab ab
ab
21
in

a
2H ay ay go.nu

2
151
0

94 tt d15I
 eg Colents
MAIL

I a'fÉ a
MI 12

dAdive fog

a m

11 2

cis CoActive m I

ft tomato 2 en pair
OActive
stereoiso 3

MCAA793 .ms

IIEEI Inactive
I A 511 lats
A b a A fatal
9 I 2
2
I 0 Total 5 I
10
M AA
92bI
A a a btblo.tn
b
a b Al a
1A
a b b A ata
active
G I 3
G Active 2

Total 5 I 4

Aa
tianya.to
Cb A 6T
on if
i A atb CAffEf
1A 9

2
O Active
totals.IE

MCAAIabLdF
g

o I 12
O Active 12
Stereoisomerism in Octahedratral Complexes
Types of Geometrical Isomers Optical Isomers Total S.I.
complex (Cis + Trans) (O.A. + O.Inactive)
[Ma4b2]n± 2(1Cis + 1Trans) No Optical Isomers 2
[Ma4bc]n± 2(1Cis + 1Trans) No Optical Isomers 2
[Ma3b3]n± 2(1Cis + 1Trans) No Optical Isomers 2
[Ma3b2c]n± 3(1Cis + 2Trans) No Optical Isomers 3
[Ma3bcd]n± 4(1Cis + 3Trans) 5(2 + 3) 5
[Ma2b2c2]n± 5(1Cis + 4Trans) 6(2 + 4) 6
[Ma2b2cd]n± 6(2Cis + 4Trans) 8(4 + 4) 8
[Ma2bcde]n± 9(6Cis + 3Trans) 15(12 + 3) 15
[Mabcdef]n± 15(Cis & trans not defined) 30(30 + 0) 30

Types of Geometrical Isomers Optical Isomers Total S.I.

complex (Cis + Trans) (O.A. + O.Inactive)
[M(AA)3]n± No Geometrical Isomers 2(2 + 0) 2
[M(AA)2b2]n± 2(1Cis + 1Trans) 3(2 + 1) 3

[M(AA)2bc]n± 2(1Cis + 1Trans) 3(2 + 1) 3

[M(AA)b2c2]n± 3(1Cis + 2Trans) 4(2 + 2) 4
[M(AA)b3c]n± 2(1Cis + 1trans) No Optical Isomers 2
[M(AA)b2cd]n± 4(2Cis + 2Trans) 6(4 + 2) 6
[M(AA)bcde]n± 6(Cis & trans not defined) 12(12 + 0) 12

Types of Geometrical Isomers Optical Isomers Total S.I.

complex (Cis + Trans) (O.A. + O.Inactive)

[M(AB)3]n± 2(1Cis + 1Trans) 4(4 + 0) 4

[M(AB)2c2]n± 5(1Cis + 4Trans) 8(6 + 2) 8
[M(AB)2cd]n± 6(2Cis + 4Trans) 11(10 + 1) 11
[M(AB)c2d2]n± 4(2Cis + 2Trans) 6(4 + 2) 6
[M(AB)c3d]n± 3(1Cis + 2Trans) 4(2 + 2) 4
[M(AB)c2de]n± 7(4Cis + 3Trans) 12(10 + 2) 12
[M(AB)cdef]n± 12(Cis & trans not defined ) 24(24 + 0) 24
Text Question : Predict possible number of GI and OI of given complexes.
(1) [M(AB)(CD)(EF)]n± 8GI 16 OI
(2) [M(AB)(CD) ef] n± 10 GI 20 OI
(3) [M(AB)(CD) (EE)]n± 4 GI 8 OI
(4) [M(AB)(CD) e2]n± 6 GI 10 OI (2 meso)
(5) [M(AB)2(CD)]n± 4 GI 8 OI
(6) [M(AB)2(CC)]n± 3 GI 6 OI
Sol.
(2)
A
B E
(1) M (2)
8GI (cis trans not defined) & 16OI
C F
(2) D
A A
f B B f
(2) (2) M + M 10GI (8cis + 2 transcis / trans defined w.r.t. e&f)
e C e D
D (2) C
A
B E
(3) M 4GI(cis-trans not defined) & 8 OI
C E
D
A e
B e A C
(4) M + M 6GI (4cis + 2trans) & 10OI (8 active + 2 inactive)
C e B D
D e
A A
B D B D
(5) M + M 4GI (2 cis + 2 trans) &8OI
A C B C
B A
A A
B C B C
(6) M + M 3GI(1 cis + 2 trans) & OI = 6
A C B C
B A

QUESTIONS FOR PRACTICE–8

1. [Pt(NH3)(NO2)Py(NH2OH)]+ will form geometrical isomers:
(A) 2 (B) 3 (C) 4 (D) 5
2. Geometrical isomerism in coordination compunds is exhibited by
(A) Square planar and tetrahedral complexes (B) Square planar and octahedral complexes
(C) Tetrahedral and octahedral complexes (D) Squre planar, tetrahedral and octahedral complexes
3. Which of the following complex ion exhibits optical activity ?
(A) cis-[Co(en)2Cl2]+ (B) [Co(NH3)4Cl2]+ (C) [Co(NH3)2Cl4]– (D) trans-[Co(en)2Cl2]+

4. Which of the following complexes exhibit optical activity?

(A) trans-tetramminedithiocyanatochromium (III) ion (B) cis-diamminedicarbonatocobaltate (III) ion
(C) trans-diamminedicarbonatocobaltate (III) ion (D) cis-diglycinatoplatinum (II)

5. In which case racemic mixture is obtained on mixing its mirror images in 1 : 1 molar ratio?
(A) [Cr(en)3]3+ (B) [Ni(DMG)2] (C) cis-[Cu(Gly)2] (D) in all cases

6. Which of the following is not optically active?

(A) [Co(en)3]3+ (B) [Cr(ox)3]3– (C) cis-[CoCl2(en)2]+ (D) trans-[CoCl2(en)2]+

_____
 1
7.
2
The complex which exhibits cis-trans isomerism as well as can be resolved into d and -forms.
(A) [Be(bcac)2] (B) [Ir(H2O)3(NH3)3]3+ (C) [Cr(en)3]3+ (D) [Rh(H2O)(py)(en)2]3+

8. Select the correct code regarding total number of space isomers for the following compounds:

(II) [M(AB)3 ]  (III) [Ma2b2c 2 ] 

n n
(I) [Ma3b2c]n
(I) (II) (III) (I) (II) (III)
(A) 4 4 6 (B) 4 3 5
(C) 3 3 5 (D) 3 4 6

9. Statement-1 : Mabcd (Tetrahedron) does not show geometrical isomerism.

Statement-2 : sp3 hybrid orbitals are at 109° 28 to one another.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.

Comprehension-1 (Q.10 to Q.12)

Complex compounds that have the same molecular formula but have different structural/space
arrangements of ligands around central metal atom / ion are called isomers, these are of two types namely
structural and stereo isomers.

10. Which is not correctly matched

(A) [Ir(CN)(H2O)5] [Ir (CN)5 (H2O)] and [Ir (H2O)6]2 [Ir (CN)5 (H2O)]3 are Polymerization isomers
(B) [Rh(en)3] [Ni(CN)5] and [Ni(en)3] [Rh(CN)5] are Co-ordination isomers
(C) [Pd(NO2) (H2O)5] [CuCl5] does not exhibit Hydrate isomerism
(D) [Pt(CO3) (en)2] Br2 exhibits Ionization isomerism

11. Which of the following complex compound is not having two stereoisomers.
(A) [Zn(gly) (CN) py] (B) [Be (acac) (H2O) (NH3)]+
(C) [Pd(gly) Br(NH3)] (D) [Be (gly)2]

12. Which of the following complex compound exhibits geometrical isomerism

(A) [Pt Br Cl (H2O) (NH3)](B) [Zn (gly)2] (C) [Pd (acac) Br(py)] (D) [Be (acac)(gly)]

Comprehension-2 (Q. 13 to Q. 15)

Co-ordination compounds exhibit both structural and stereoisomerism. Structures are possible due to different
bonds between central metal and ligands. But in stereoisomers same bonds are presents and it is different
in orientation of bonds, different stereoisomers are formed.

13. Which of the following complex compound can exhibit total two co-ordination isomers and is polymer isomer
of [Ir Br2(H2O)4] [IrBr4(H2O)2]

(A) [Ir (H2O)6]2 [Ir Br5(H2O)]3 (B) [Ir(H2O)6] [IrBr4(H2O)2]4

(C) [IrBr(H2O)5] [IrBr5(H2O)] (D) [Ir(H2O)6]2 [IrBr6]

14. Which of the following complex compound can exhibit structural isomerism and at least its one configuration
is optically active and other is optically inactive.
(A) [CoBr2(en)2]Br (B) [Ir (CO3) (H2O)2(NH3)2]Cl
(C) [Cr(acac) (en)2] C2O4 (D) [RhBr(gly)(H2O)3](NO2)

15. Which of the following complex species does not exhibit structural isomerism.
(A) [PtBr2(en)2] Cl2 (B) [Ir (ONO) (en) (H2O) (py)]2+
(C) [Pd(NH3)4] [PdCl4] (D) None of these
 It 1 4 doe
16. Aqueous solution of Ni2+ contains [Ni(H2O)6]2+
and its magnetic moment is 2.83 B.M. When excess CN– ion
is added in it, comment on the magnetic moment of solution
(A) It will remain same (B) It increases from 2.83 B.M.
(C) It decreases from 2.83 B.M. (D) It can not be predicted theoretically

Hiiiii Y
17. Consider the following reaction :
 gly
[M(gly)(NH3 )2 ]   [M(gly )2 ]0
– 2NH3

If product exists in two stereoisomeric forms then hybridization of metal M in the product will be

(A) sp3 only (B) dsp2 only (C) either sp3 or dsp2 (D) No hybridization

18. Compound 'X' has molecular formula CrCl2Br . 6H2O, can show type of isomerism.
(i) hydrate isomerism (ii) ionization isomerism
(iii) geometrical isomerism (iv) optical isomerism
(A) (i) (ii) and (iii) only (B) (i) and (ii) only (C) (i), (ii), (iii) and (iv) (D) (i) and (iii) only

One or more than one correct :

19. Consider the following representation for complex compound “Triaquatrichlororuthenium (III)
T
X1

X6 X2
M
X5 X3

X4
Where, M = Ru and X1 to X6 are donating sites either of ‘O’ or ‘Cl’ atoms of ligands. Then correct statement(s)
according to given information is/are
(A) If X1, X2 and X3 positions are occupied by more electronegative donar ‘O’ atom of ligands then it represents
facial isomer.
(B) If X2, X3 and X5 positions are occupied by more electronegative donar ‘O’ atom of ligands then it represents
meridional isomer.
(C) If X2, X4 and X6 positions are occupied by less electronegative donar ‘Cl’ atom of ligands then it represents
facial isomer.
(D) If X4, X5 and X6 positions are occupied by less electronegative donar ‘Cl’ atom of ligands then it exhibits
optical isomerism.
20. Which of the following compound(s) show optical isomerism?
(A) cis–[Co(NH3)4Cl2]+ (B) trans–[Co(en)2Cl2]+ (C) cis–[Co(en)2Cl2]+ (D) [Co(en)3]3+

21. Which of the following compounds can not have optically inactive isomer.
(A) [Fe(en)3]3+ (B) [Pt (Br) (Cl) (I) (NO2) (H2O) (NH3)]
(C) [Cr(gly)3] (D) [Co(C2O4)(NO2)(NH3)3]

22. Which of the following statements is/are false

(A) In [PtCl2(NH3)4]2+ complex ion, the cis-form is optically active, while trans-form is optically inactive
(B) In [Fe(C2O4)3]3–, geometrical isomerism does not exist, while optical isomerism exists
(C) [Mabcd]n square planar complexes exhibit both optical as well as geometrical isomerism
(D) In [Mabcd]n± tetrahedral complexes, optical isomerism cannot be observed
 non
23. Which of the following complexes can exist as diastereoisomers?
(A) [Cr(NH3)2Cl4]– (B) [Co(NH3)5Br] 2+ (C) [FeCl2(SCN)2]2– (D) [PtCl2Br2]2–
24. Isomers of complex ion (I) can form three complex ions on reaction with neutral symmetrical bidentate
ligand (AA).
+AA [M(AA)2c2]
n±

–2b Complex ion (II)

[M(AA)b2c2]
n± +AA [M(AA)2b2]
n±
(Here b, and c are monodentate ligands)
–2c
Complex ion (I) Complex ion (III)

+AA [M(AA)2bc]
n±

–b, –c Complex ion (IV)

Then according to the given information the correct statement(s) is/are
(A) If an isomer of complex ion(I) can form all three complex ions (II, III and IV), then it is in cis-form
(B) If an isomer of complex ion (I) can form two complex ions (II and IV), then it is in trans-form
(C) If an isomer of complex ion (I) can form only two complex ions (III and IV), then it is optically inactive
(D) If an isomer of complex ion (I) can form only two complex ions (II and III), then it is optically inactive

25. A complex compound (x) of Co3+ cation; contains ammonia, chloride ions and water molecules in ratio of
4 : 3 : 1. One mole of the complex compound gives two moles of AgCl  with excess of AgNO3 solution. Then
correct statement(s) regarding the complex compound is/are
(A) The complex compound can show geometrical isomerism.
(B) The magnetic moment of complex compound is not equal to zero.
(C) The complex compound is [Co(H2O) (NH3)4Cl]Cl2.
(D) The complex compound does not show optical isomerism.

26. The degeneracy of d-orbitals is lost under

(A) Strong field ligand (B) Weak field ligand
(C) Mixed field ligand (D) Chelated ligand field

Match The column:

27. Column I Column II
(Co-ordination compound) (Type of isomerism shown)
(A) Na2[Pt(SCN)2(Ox)2] (P) Ionization isomerism
(B) [CrCl2(NH3)4]NO3 (Q) Linkage isomerism
(C) [Pt(NO2)(Gly)(NH3)] (R) Geometrical isomerism
(D) K3[Fe(OH)2(C2O4)2] (S) Optical isomerism

28. Column-I Column-II

(A) Difference between number of cis and trans isomers is equal to 3 (P) [Ma2b2c2]n±
(B) Difference between number of optical active and inactive isomers (Q) [Ma2bcde]n±
is equal to 9
(C) All trans isomers are optically inactive (R) [M(AB)2c2]n±
(D) Odd number of stereo (space) isomers (S) [M(AB)2cd]n±
(T) [Ma3bcd]n±

(Where a, b, c, d and e are Monodentate ligands and AB is unsym. bidentate ligand)

 29. Column-I Column-II
(A) [Co(gly)(SCN)(en) (H2O)] (P) Linkage isomerism
(B) [CrBr2(NO2)2(H2O)(NH3)]– (Q) Polymerisation isomerism
(C) [IrCl2(gly)(OCN)(py)]– (R) Only one trans configuration is optically active
(D) [Fe(NCS)(OX)(NH3)2(py)] (S) Cis configurations are greater than trans configurations
(T) All trans configuration(s) are optically inactive

30. Match the column-I with column-II.

Note that column-I may have more than one matching options in column-II.
Column-I Column-II
(A) [Cr(gly)3]° (P) Low spin complex
(B) [CoBr2Cl2]2– (Q) high spin complex
(C) [Fe(NH3)6]3+ (R) optical isomerism
(D) Na[PtBrCl(NO2)(NH3)] (S) geometrical isomerism

Subjective :
31. Total number of complexes among the following which are optically active ?
(i) [Cr(ox)3]3– (ii) cis-[Pt(Cl2)(en)] (iii) cis-[Rh(Cl2)(NH3)4]+
(iv) [Ru(dipy)3]3+ (v) cis-[Co(NO2)3(dien)] (vi) Trans-[Co(NO2)3(dien)]
(vii) cis-[Co(NO2)3 (NH3)3]

32. Find out value of expression |x – y| for complex compound [Zn (bcac)2]
where, x = Total number of O – Zn – O bond angle(s) in the compound
y = Total number of sp3 Hybridized atom(s) in the compound

33. Consider the following complexes.

(i) [Fe IF(CN) (H2O) (en)]
(ii) [Mo Cl2F2(gly)]2–
Then calculate value of |x – y| (where x and y are total number of possible optically active isomers in (i) and
(ii) complex respectively).

PRACTICE–7

1. D 2. D 3. B 4. D 5. D 6. C 7. B
8. 8

PRACTICE–8

1. B 2. B 3. A 4. B 5. A 6. D 7. D
8. D 9. A 10. B 11. B 12. A 13. A 14. D
15. B 16. A 17. C 18. A 19. ABC 20. CD 21. ABC
22. ACD 23. AD 24. ABC 25. ACD 26. ABCD
27. A Q, R, S ; B  P, R; C  Q, R; D  R, S
28. A  P, Q, R ; B  Q, S ; C  P, Q, T ; D Q, S, T ;
29. A  P, Q, R, S ; B  P, T ; C  P, R, S ; D P, Q, T ;
30. A  R.S.; B  Q; C  P; D P,S,
31. 2 32. 1 33. 8