Coordination Compounds

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Chemistry
ALLEN
UNIT-9 : COORDINATION COMPOUNDS
UNIT INDEX
• Theory 262-277
• Exercise-1_Intext Questions 278-282
• Exercise-2_NCERT Exercise Questions 283-299
• Exercise-3_Exemplar 300-305
• Exercise-4_MCQ, A/R, Case Based Questions 306-313
• Previous Years Questions 314-324
• Practice Test 325-328
THEORY
INTRODUCTION
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(a) The concept of coordination compounds arises from the complex formation tendency of transition
elements.
(b) These compounds play a vital role in our lives. Haemoglobin of blood and chlorophyll of plants
are also coordination compounds of Fe, Mg respectively.
TYPE OF COMPOUNDS
Molecular or Addition Compounds
(a) When two or more simple salts are chemically combined together in fixed proportion by weight
the molecular or addition compounds are formed.
(b) Some common examples are as follows.
K2SO4 + Al2(SO4)3 + 24H2O K2SO4.Al2(SO4)3.24H2O
Alum
(c) Depending upon the behavior in an aqueous solution they are of two types
(i) Double salt (ii) Coordination or complex compounds.
(I) Double Salt
The addition compounds which loose their identity in aq. solution and get completely ionised in
water and give positive test of their constitute ions.
Ex. (i) K2SO4.Al2(SO4)3.24H2O (Potash Alum)
(ii) FeSO4(NH4)2SO4.6H2O (Mohr's salt)
(iii) KCl.MgCl2.6H2O (Carnallite)
KCl.MgCl2.6H2O 
H2O
 K+ + Mg2+ + 3Cl–
(II) Coordination or Complex Compounds
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(a) Those molecular or addition compounds which retain their identity in aq. solution or loose
the identity of constituents are called complex salt.
(b) Complexes retain their identity in aqueous solution. i.e., they do not dissociate into separate
ion.
K 4 [Fe(CN)6 ] 
H2 O
 4K   [Fe(CN)6 ]4
Potassium ferrocyanide Ferrocyanide ion
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(c) On the basis of type of ligands complex compounds are divided as follows :
(i) Homoleptic complexes :
Complex in which all the ligands are identical is called homoleptic complex.
Ex. [Co(NH3)6]+2
(ii) Heteroleptic complexes :
Complex in which all the ligands are not identical is known as heteroleptic complex.
Ex. [Fe(en)2Cl2]+1
TERMINOLOGY OF COMPLEX COMPOUNDS
(a) Complex Ion/Coordination sphere
• An aggregate of metal ion with anions, cation or neutral molecules is called as complex
ion.
• It is a non ionisable part of complex compound.
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(b) Central Metal Ion
(i) The metal ion which forms complex ion in combination with anions, cation or neutral
molecules is called as central metal ion.
(ii) Central metal ion acts as an electron pair acceptor and forms coordinate bonds with donor
species.
(iii) Generally belongs to d block because d block elements have tendency to form complex due
to their high charge density and availability of vacant orbitals.
(c) Coordination Number
The total number of coordinate bonds formed by central metal ion with donor species is called as
coordination number of central metal ion.
(d) Ionisation Sphere
The part of complex compound which get ionised is known as ionisation sphere.
Central metal ion Coordination sphere
[Cu(NH3)4]SO4 Ionization sphere/Counter ion
Ligand Coordination number
(e) Oxidation State

It is a number which represents the electrical charge on the central metal atom of a complex ion.
Ex. the oxidation number of Fe, Co and Ni in [Fe(CN)6]4—, [Co(NH3)6]3+ and Ni(CO)4 is +2, +3
and zero respectively.
(f) Charge On the Complex Ion
It is the algebraic sum of the total charge of the donor species and central metal ion.
(g) Ligands
(i) The anions, cation or neutral molecules which combine with central metal ion to form
complex ion are called as ligands.
(ii) They act as electron pair donor (Lewis bases) which donate e– pair to central metal ion and
form coordinate bonds.
(iii) no. of e– pair donated by a ligand to central metal ion is equal to its denticity.
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(h) Naming of ligands

(i) o-suffix is used in the name of anionic ligands.
(ii) ium-suffix is used in the name of cationic ligands.
Classification of ligands :
On the basis of denticity :
1. Monodentate ligands : Which donate one e– pair to the central metal ion.
Neutral monodentate ligands
NH3 ammine
H 2O aqua
NO nitrosyl
PH3 phosphine
PPh3 triphenyl phosphine
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O2 dioxygen
N2 dinitrogen
CH3–OH methyl alcohol
CH3–NH2 methyl amine
NH2CONH2 urea
NH2NH2 hydrazine
CH3–O–CH3 dimethyl ether
CO carbonyl
CS thiocarbonyl
Cationic monodentate ligands :

+
O2 oxygenium
NO+ nitrosylium or nitrosonium
NO2+ nitronium
hydrazinium
H2 N N H3
Anionic monodentate ligands :

–
F Fluorido / fluoro
Cl– Chlorido / chloro
Br– bromido / bromo
I– iodido / iodo
O–2 oxido/oxo
S–2 sulphido/sulpho
OH– hydroxido / hydroxo
O 2– superoxido / superoxo
O2–2 peroxido / peroxo
N–3 nitrido
N3– azido
(NH2)– amido
NH–2 imido
H– hydrido
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2. Bidentate ligands : Ligands which donates two e– pair to the central metal ion.
Ligands having denticity 2 or more than 2 form a stable ring with central metal ion that's why
they are known as chelating ligands.
no. of rings = Denticity – 1
O O
NH2 CH2 CH2 NH2
N N M+
O O
M+ M+
Ethylene diamine (en) dipyridyl(dipy) oxalato(ox) or C2O4–2
O H
H2N CH2 C O
CH3 C CH C CH3 CH3 C N
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O
O O M+
M + CH3 C N
glycinato(gly) M+ O
(unsymmetrical) acetyl acetonato (acac)– dimethyl glyoximato(dmg)–
3. Polydentate ligands
CH2 CH NH CH2 CH CH2–CH2–NH–CH2–CH2–NH–CH2–CH2
H2 N NH2 H2N NH2

+
M
+
M
Diethylenetriamine(dien) Triethylenetetraamine (trien)
Tridentate Tetradentate
OOC CH2 CH2 COO

N CH2 CH2 N
OOC CH2 CH2 COO
4–
Ethylene diaminetetraacetato (EDTA )
Hexadenatate
4. Ambidentate ligand : Ligands which have two different donor atoms but at one time one donor
atom can donate electron pair are called ambidentate ligands.
Ambidentate ligands have same molecular formula but have different donor atom.
(i) M C N cyanido (CN)
M N C isocyanido(NC)
(ii) M O C N cyanato / cyanato-O
M N C O isocyanato / cyanato-N
(iii) M S C N Thiocyanato / Thiocyanato-S
M N C S Isothiocyanato/thiocyanato-N
(iv) M O N O Nitrito / Nitrito-O
O
M N
O Nitro / Nitrito-N
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ALLEN
Synergic bonding:-
(a)  donor and acceptor ligands
Ligands which donate their lone pair to central metal ion through  bond and simultaneously
accept e– pair from central metal ion through  bond.
The electronic configuration of CO molecule shows that it has lone pair of electrons on carbon
and oxygen atom each. Carbon atom can donate its electron pair of a transition metal atom (M),
forming OCM coordinate bond.
Since the metal atom in metal carbonyl is in zero oxidation state, the formation of M  CO 
bond accumulates a negative charge on the metal atom. The accumulation of negative charge on
the metal atom can be counter balanced by transferring some negative charge from the metal
atom to CO molecule (ligand). This transfer can be done by making a M  CO  bond by the
overlap between an appropriate filled d orbital on the metal atom and empty y or z molecular
orbital of CO molecule. This type of bonding between M and CO is called synergic bonding.
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– M + + C  O  – M 
C O   bond
– +  bond / back bond

–
+ – –
 formed by full filled
M C O M CO 

d orbital of M and
+ + Vacant * 2p orbital of CO
+
+ – –
[Schematic of orbital overlaps in metal carbonyls]
Conclusion of synergic bonding :

(a) M–C bond strength increases; M–C bond length decreases; because double bond character
increases
(b) C–O bond strength decreases; C–O bond length increases; because bond order of C–O
decreases (CO accepts e– pair into its antibonding molecular orbital)
IUPAC NOMENCLATURE OF COORDINATION COMPOUNDS
Complex Compounds IUPAC Name
(i) K4[Fe(CN)6] Potassium hexacyanidoferrate (II)

(ii) K2[HgI4] Potassium tetraiodidomercurate (II)
(iii) [Co (NH3)6] Cl3 Hexamminecobalt (III) chloride
(iv) [Cr(H2O)4Cl2] Cl Tetraaquadichlorochromium (III) chloride
(v) [Pt(NH3)2Cl4] Diammine tetrachloroplatinum (IV)
(vi) [Co(NH3)3 Cl3] Triamminetrichlorocobalt (III)
(vii) K3[Co(NO2)6 ] Potassium hexanitrocobaltate (III)

(viii) Na2[Fe(CN)5 NO] Sodium pentacyanonitrosoniumferrate (II)
(ix) [NiCl4]–2 Tetrachloronickelate (II) ion
(x) [Ru(NH3)5Cl]+2 Pentamminechlororuthenium (III) ion
(xi) [Fe(en)3]Cl3 Tris (ethylenediamine) iron (III) chloride
(xii) [Ni (Gly)2 ] Bis (glycinato) nickel (II)
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BONDING IN COORDINATION COMPOUNDS
(A) WERNER'S THEORY
This was postulated by Alfred Werner in 1893. The postulates of Werner's theory of complexes
are –
According to Werner central metal atom in a complex compound have 2 types of valencies :
Primary valencies Secondary valencies
(i) Equal to oxidation state of CMA (i) Equal to coordination number of CMA
(ii) Satisfied by anions (ii) satisfied by ligands
(iii) Non directional (iii) Directional
(iv) Ionisable (iv) Non-ionisable
(v) not helpful in geometry prediction of (v) helpful in geometry prediction of
complex ion complex ion
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Experimental evidence of werner's theory
(a) Precipitation of primary valencies on the addition of suitable reagent. In a series of compounds
of cobalt (III) chloride with ammonia, it was found that some of the chloride ions could be
precipitated as AgCl on adding silver nitrate solution but some remained in solution.
AgNO3
1 mole CoCl3 6NH3 3 moles of AgCl
white ppt
Hence CoCl3 6NH3 is formulated as [Co(NH3)6]Cl3, which ionises as [Co(NH3)6]+3 + 3Cl–
(4 mole ions)
AgNO3
hence CoCl3 5NH3 is formulated as [Co(NH3)5Cl] Cl2, which ionises as [Co(NH3)5Cl]+2 + 2Cl–
(3 mole ions)
AgNO3
hence CoCl3 4NH3 is formulated as [Co(NH3)4Cl2] Cl, which ionises as [Co(NH3)4Cl2]+ + Cl–
(2 mole ions)
(B) VALENCE BOND THEORY
This theory was mainly developed by Linus Pauling. The main features of this theory are -
(a) Metal ion when it forms a complex compound undergoes formation of coordinate bond.
(b) During this bond formation, the metal ion acts as electron pair acceptor. For this the metal
ion provides vacant orbitals according to its coordination number.
Ex. In the formation of [Fe(NH3 )6 ]3+, Fe+3 ion provides six vacant orbitals.
In [Cu(NH3 )4 ]2+, Cu+2 ion provides four vacant orbitals.
(c) These vacant orbitals undergo hybridisation before bond formation with ligands.
(d) The vacant hybrid orbitals of metal ion get overlapped with orbitals of ligands containing
lone pair of electrons.
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(e) If in a complex strong ligand is present then it will cause pairing of unpaired e– in (n–1)d
orbitals of central metal ion and if (n–1)d orbitals are involved in hybridisation then inner
orbital complex is formed.
(f) If in the complex weak ligand is present then there will be no pairing of unpaired e– in
(n–1)d orbitals and if nd orbitals are involved in hybridisation, outer orbital complex is
formed.
(g) If unpaired e– is present in the complex then it will be paramagnetic otherwise it will be
diamagnetic.
Applications of valence bond Theory
(a) 6-coordinated complexes :
[Co(NH3 )6 ]3+
e– configuration of 27Co = [Ar] 3d7 4s2 So, Co+3 = [Ar] 3d6 4s° 4p° 4d°
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Co3+ =
3d 4s 4p 4d
Due to presence of strong ligand unpaired electrons get paired up so metal ion provides vacant
'3d' orbitals for hybridisation.
3d 4s 4p 4d
2 3
d sp hybridisation
This is a diamagnetic complex.

As inner 'd' orbitals are involved in hybridisation, hence it is an inner orbital complex.
[CoF6]3–
e– configuration of Co27 = [Ar] 3d74s2 Co+3 = [Ar] 3d6 4s0 4p0 4d0
Co3+ =
F– is a weak ligand, so unpaired e– do not get paired up and vacant 4d orbitals
involved in hybridisation.
3d 4s 4p 4d
sp3d2
This is a paramagnetic complex.

The outer 'd' orbitals are involved in hybridisation, hence it is an outer orbital complex.
(b) 4-coordinated complexes :
[NiCl4]2–
e– configuration of 28Ni = [Ar] 3d8 4s2

Ni+2 = [Ar] 3d8 4s0 4p0
There will be no pairing of unpaired e– in 3d orbitals.
3d 4s 4p
3
sp hybridisation
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[NiCl4]2— has tetrahedral geometry.
It is a paramagnetic complex.
[Ni (CN)4]2–
8 2
28Ni = [Ar] 3d 4s Ni+2 = [Ar] 3d84s04s0
CN– is a strong ligand so unpaired e– in 3d orbitals get paired up
3d 4s 4p
dsp hybridisation
2
2–
[Ni(CN)4] has square planer geometry and diamganetic in nature.
This complex is an inner orbital complex
[Zn(NH3)4]2+
Zn = [Ar] 4s2 3d10
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Zn+2 = [Ar] 3d104s04p0
Zn+2 has d10 configuration
So there is no possibility of pairing
3d 4s 4p
sp3
Because the complex is formed by sp3 hybridisation, hence it has tetrahedral geometry.
Since all electrons are paired, hence it is diamagnetic
[Ni(CO)4]
Ni = [Ar] 3d8 4s2 4p°
CO is a strong ligand so unpaired e– in (n–1)d orbitals get paired up.
Ni =
3d 4s 4p
3
sp hybridisation
3
Complex has sp hybridisation
It has tetrahedral geometry.
It is diamagnetic complex as unpaired e– is absent.
[Cu(NH3)4]2+
1 10
29Cu = [Ar] 4s 3d Cu+2 = [Ar] 3d9 4s0 4p0
NH3 is a strong ligand so after rearrangement
Complex has dsp2 hybridsation
It is inner orbital complex

It has square planer geometry
It is paramagenetic
3d 4s 4p
2
dsp
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(C) Crystal field theory

Crystal Field Theory : This is a model of electronic structure of transition-metal complexes that
considers how the energies of the d-orbitals of a metal ion are affected by the electric field of the
ligand. According to this theory.
(a) Central metal ion is considered as a positive point charge, anionic ligand as a negative
point charge, neutral ligand as a point dipole and attraction between metal ion and ligand is
electrostatic in nature.
(b) In the electric field of ligands, the five d orbitals of the metal atom no longer have exactly
same energy while they are splitted into different energy levels. Splitting of five degenerate
d-orbitals of the metal ion into t2g and eg sets of orbitals having different energies is called
crystal field splitting.
(c) The extent of splitting of metal d-orbitals depends upon the nature and number of ligands
surrounding it and the charge on the central metal ion.
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(d) The extent of splitting of metal d-orbitals determines the magnetic and spectroscopic
properties of the complexes.
SPLITTING IN OCTAHEDRAL COMPLEXES
In a octahedral complex, the co-ordination number is 6. The metal ion is at the centre and the
ligands occupy the six corners of the octahedron as shown in figure.
We know that two orbitals, d x y and d z are oriented along the axis while the remaining three
2 2 2
orbitals, viz., dxy, dyz and dzx are oriented in between the axis.
Z
L L L
X
L
Y L
The two orbitals d x 2

y2
and d z are designated as eg orbitals while the three orbitals dxy, dyz and dzx
2
are designated as t2g orbitals. As the six ligands approach the central ion along the axis hence e g
orbitals, is repelled more by the ligand than the t2g orbitals.
In other words, the energy of the eg orbitals increases much more than the energy of the t 2g
orbitals.
Thus, in octahedral complexes, the five d-orbitals split up into two sets : one set consisting of two
orbitals ( d x -y and d z ) of higher energy (eg orbitals) and the other set consisting of three orbitals
2 2 2
(dxy, dyz and dzx) of lower energy (t2g orbitals).

eg
0.6
= crystal field splitting
–0.4 energy of octahedral complex
State II t2g
State III
State I
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Splitting in tetrahedral complex
The co-ordination number for tetrahedral complexes is 4. The tetrahedral arrangement of four
ligands surrounding a metal ion may be visualized by placing ligands at the alternate corners of a
cube, as shown in figure.
Z
L
L
M+ X
L
Y L
Tetrahedral arrangement
of four lignads
It can be shown that in a tetrahedral structure, none of the d-orbitals points exactly towards the
ligands.
When ligand approaches it is more close dxy, dyz, dxz in comparision of d x y and d z because dxy, 2 2 2
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dyz, dzx are between the axis and d z and d x 2 2
y2
are along the axis. So dxy, dyz, dzx feels more
repulsion as compare to d z and d x 2 2
y2
.
Thus, the d orbitals are also splitted into two groups but in a reverse order of octahedral complex.
The three orbitals, dxy, dyz and dxz, designated are now have higher energy than the two orbitals
d x y and d z .
2 2 2
t2g
0.4 t
= Spitting energy of tetrahedral complex
State II –0.6 t
t
eg
State I State III
Calculation of crystal field stablizing energy (CFSE)

For octahedral complex CFSE = –0.4 n t 2g
0.6 neg 0 + Pairing energy (P.E.)
where n t = number of electron in t2g orbitals
2g
n eg = number of electron in eg orbitals

= crystal field splitting energy
0
Factors affecting splitting energy ( )

(i) Strength of ligand [C.F.S.E. is more in case of S.F.L. as compared to W.F.L.]
(ii) Oxidation state of central metal ion [C.F.S.E. oxidation state]
(iii) Transition series (d-series) [C.F.S.E. , 5d > 4d > 3d]
(iv) Geometry [ sp > 0 > t]
(v) number of ligands

4 4
sp= 0 t= 0
3 9
Spectro-chemical series for ligands
Series which shows the relative strength of ligands
I–(weakest) < Br– < SCN– < Cl– < S–2 > F– < OH– < C2O42– < H2O < NCS–
< edta4– < NH3 < en < NO2– < CN– < CO(strongest)
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APPLICATION OF CRYSTAL FIELD THEORY

Applications of C.F.T are
(i) To explain weather complex is high spin or low spin complex.
(ii) To explain colour property
(iii) To explain stability of complex
(II) COLOUR PROPERTY OF COMPLEX COMPOUNDS :
Reason for colour in complexes is due to d-d-transition
eg
1
eg
0
energy
d-d transition
0
t2g
1
t2g
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ground state excited state
P V I
R B
Commentary colour wheel O
For example complementary colour of red is blue
BG
Y
YG
green.
(III) STABILITY OF CO-ORDINATION COMPOUNDS
According to thermodynamic stability, the reaction between a metal ion and the ligands may be
considered as a Lewis acid base reaction. If the equilibrium constant is high then the
complex obtained is theromodynamically stable. The reaction can be written as follows :
M + nL [MLn]
[ML n ]
The stability constant K, of the complex [MLn] is given by the relation, K = . The greater
[M][L]n
the value of K, more stable is the complex.
The stability of a complex ion also depends upon –
(i) Higher charge of the central metal ion.
(ii) Greater strength of the ligand.
(iii) Ring formation (chelation) in structure of complexes.
ISOMERISM IN COMPLEXES
Compounds which have the same molecular formula, but differ in their properties due to the
difference in their structure are called as Isomers.

Classification of isomerism :
Type of isomerism
(A) Structural isomerism (B) Stereo isomerism
Ionization Hydrate Coordination Linkage Geometrical Optical

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(A) Structural Isomerism
It arises due to the difference in the type of chemical linkages and distribution of ligands within
and outside the coordination sphere.
(i) Ionisation Isomerism
Compounds having same molecular formula but give different type of ions in their aqueous
solution are known as ionisation isomer.
Due to exchange of ions between coordination sphere and ionisation sphere different ionisation
isomers are formed. So they are ionisation isomers.
Ex. (a) CoBrSO4 5NH3 can represent
(i) [Co(NH3)5Br] SO4 (red violet)
(ii) [Co(NH3 )5 SO4 ] Br (red).
These complexes give sulphate ion and bromide ion respectively
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(b) [Pt(NH3)4Cl2] Br2 and [Pt(NH3 )4Br2]Cl2
(c) [Co(NH3)4(NO3)2 ]SO4 and [Co(NH3)4SO4](NO3)2
(ii) Hydrate Isomerism
This type of isomerism is due to presence of different number of water molecules inside the
complex ion.
Ex. (a) Cr(H2O)6Cl3 has three possible hydrate isomers.
(i) [Cr(H2O)6]Cl3 (violet)
(ii) [Cr(H2O)5Cl] Cl2 .H2O (green)
(iii) [Cr(H2O)4Cl2]Cl . 2H2O (dark green)
These complexes differ from one another with respect to the number of water molecules acting as
ligands.
(iii) Linkage Isomerism
(a) This type of isomerism arises due to presence of ambidentate ligands
(b) These ligands have two donor atoms but at a time only one atom is directly linked to the
central metal atom of the complex.
Ex. [Co(NH3)5NO2]Cl2 and [Co(NH3)5 ONO]Cl2
In NO2– ligand, the donor site is nitrogen while in ONO– ligand donor site is oxygen.
(iv) Coordination Isomerism
(a) This type of isomerism is exhibited when in complex compound both cation as well as anion is
complex.
(b) This type of isomerism is caused by the interchange of ligands between the two complex
ions of a complex compound.
Ex. (i) [Zn(NH3 )4 ZnCl 4 ]

Coordination isomers
(ii) [Zn(NH3 )3 Cl ZnCl 3 (NH3 )]
(B) Stereo Isomerism

(a) They have same molecular formula, same constitution but they differ only with respect to
the spatial orientation of ligands in space around the metal ion.
(b) The two types of stereo isomers which are possible are - Geometrical and optical.
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(i) Geometrical Isomerism

(a) Due to change in relative positions of ligands around central metal ion, different forms are
obtained which are known as GI.
(b) When two identical ligands are coordinated to the metal ion from same side then it is
cis isomer. (Latin, cis means same).
(c) If the two identical ligands are coordinated to the metal ion from opposite side then it is
Trans isomer (in Latin,Trans means across).
(d) These geometrical isomers differ in physical as well as in chemical properties.
(e) Geometrical isomerism is most important in compounds with coordination numbers
4 and 6.
(f) 4-coordinated complexes with tetrahedral geometry do not exhibit cis - Trans isomerism,
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because relative position of ligands remain same for each other.
(g) It is exhibited by 4-coordinated complexes with square planar geometry.
Note : There are only 5 possible cases which shows geometrical isomerism in square planar
complex. such as Ma2 b2, Ma2bc, Mabcd, M(AB)2, M(AB)cd
Geometrical Isomers With Coordination Number = 4 (Square Planar Complexes)
(i) Complexes with general formula, Ma2b2 (where both a and b are monodentate) can have
Cis-and trans isomers.
a a a b
M M
b b b a
Cis-isomer Trans-isomer
Ex. [Pt (NH3)2Cl2]

H3N NH3
Cl NH3
Pt
Pt
Cl Cl
cis-platin H3 N Cl
(used as a anti cancer) Trans-platin
(ii) Complexes with general formula Ma2bc can have Cis - and trans-isomers.
a a a c
M M
b c b a
Cis trans
eg. [Pt(NH3)2ClBr]
Cl NH3 Br NH3
Pt Pt
Br NH3 H3N Cl
Cis Trans
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(iii) Complexes with general formula, Mabcd can have three geometrical isomers.
eg. [Pt(NH3) (Py) ClBr]
a b a d a c
M M M
d c c b b d
(i) (ii) (iii)
(iv) Complex with general formula [M(AB) 2] have 2 geometrical isomers (Where AB is
unsymmetrical Bidentate ligand)
eg. [Pt(gly)2]
CH2 NH2 NH2 CH2 CH2 NH2 O CO
Pt Pt
CO O O CO CO O NH2 CH2
(cis) Trans
(v) Complex with general formula M(AB)cd can have two geometrical isomers (Where AB is
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unsymmetrical Bidentate ligand)
eg. [Pt(gly)(NH3)Br]
A c A d
M M
B d B c
(i) (ii)
Geometrical isomers with Coordination number = 6 (Octahedral complex)

(i) [Ma4b2] has 2 geometrical isomers
eg. [Fe(NH3)4Cl2]
Cl Cl
2+ +2
NH3 Cl
H3 N H3 N
Fe Fe
NH3 NH3
H3 N H3 N
Cl NH3
Trans Cis
(ii) [Ma4bc] has 2 geometrical isomers

eg. [Fe(NH3)4ClCO3]
Cl Cl
+3
CO3 +3 NH3
H3 N H3 N
Fe Fe
NH3 NH3
H3 N H3 N
NH3 CO
Cis Trans
(iii) Facial and Meridional isomerism (Ma3b3 )

eg. [Cr(NH3)3(H2O)3]+3
b b
a b a
b
a
b a a
a
b
Facial (fac) Meridional[Mer]
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(B) Optical Isomers

(a) Compounds which are mirror image of each other but non superimposable, are known as
optical isomers.
(b) An optically active complex is one which is asymmetric in nature i.e., not divisible into two
identical halves.
(c) The complex which rotates plane polarised light to left hand side is laevo rotatory i.e. ' '
or '–' and if the complex rotates the plane polarised light to right hand side then it is dextro
rotatory 'd' or '+'.
(d) Thus complexes which have same physical and chemical properties but differ in their
action towards plane polarised light are called as optical isomers.
(e) The 'd' and ' ' isomers of a compound are called as Enantiomers.
®
Optical isomers with Coordination number = 6
(i) [M(AA)3]n+ [Co(en)3]3+
3+ 3+
en en
en en
Co Co
en en
d-form Mirror -form
(ii) [M(AA)2ab]n+ [Co(en)2NH3Cl]2+

2+ 2+
en en
Cl Cl
Co Co
H3N NH3
en en
Mirror Cis- -isomer
Cis-d-isomer
APPLICATION OF COORDINATION CHEMISTRY

(a) In photography : undecomposed AgBr (at the time of image development) is removed from
photographic film by using hyposolution [Na2S2O3.5H2O]
h 1
AgBr Ag Br2
2
3
AgBr 2Na2 S2 O3 Na 3 Ag S2O3 2
NaBr
(undecomposed) so luble complex
(b) Light blue colour of aqueous solution of CuSO4 turn into dark blue in presence of ammonia
4NH 3
Cu H2O 4
SO 4 Cu NH3 4
SO 4
light blue dark blue
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(c) cyano complex are used for electroplating of Ag or Au due to high stability.
e.g. [Ag(CN)2]–
(d) Wilkinson catalyst [RhCl(PPh3)3] is used for hydrogenation of alkene. (Homogeneous catalysis)
(e) [EDTA]4– is used for estimation of hardness of water.
(f) [Ca(EDTA)]2– is used to remove Pb poison.
[Ca(EDTA)]2– + Pb+2 [Pb(EDTA)]2– + Ca+2
(g) Biological importance
Chlorophyll (Mg) haemoglobin (Fe+2) Insulin (Zn)
Vitamin B12(Co) Corboxypeptide (Zn)
®
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EXERCISE-1 INTEXT QUESTIONS

Q.1 Write the formulas for the following coordination compounds :
(i) Tetraamminediaquacobalt(III) chloride
(ii) Potassium tetracyanonickelate (II)
(iii) Tris (ethane-1,2-diamine) chromium(III) chloride
(iv) Amminebromideochloridonitrito-N-platinate(II)
(v) Dichloridobis(ethane-1,2-diamine)platinum(IV) nitrate
(vi) Iron(III) hexacyanoferrate(II)
Ans. (i) Co(H 2O) 2 (NH 3 ) 4 Cl3 (ii) K2[Ni(CN)4]
(iii) Cr(en)3 Cl3 (iv) Pt(NH)3 BrCl(NO2 )

(v) PtCl2 (en) 2 (NO3 ) 2 (vi) Fe 4 Fe(CN) 6 3
®
Q.2 Write the IUPAC name of the following coordination compounds :
(i) Co NH3 6
Cl3 (ii) Co NH3 5 Cl Cl2
(iii) K3 Fe CN 6
(iv) K 3 Fe C2O4 3
(v) K 2 PdCl4 (vi) Pt(NH 3 ) 2Cl(NH 2CH 3 ) Cl

Ans. (i) Hexamminecobalt(III) chloride
(ii) Pentaamminechloridocobalt(III) chloride
(iii) Potassium hexacyanoferrate(III)
(iv) Potassium trioxalatoferrate(III)
(v) Potassium tetrachloridopalladate(II)
(vi) Diamminechlorido(methylamine)platinum(II) chloride
Q.3 Indicate the types of isomerism exhibited by the following complexes and draw the structures for
these isomers :
(i) K[Cr(H2O)2(C2O4)2 (ii) [Co(en)3]Cl3
(iii) [Co(NH3)5(NO2)](NO3)2 (iv) [Pt(NH3)(H2O)Cl2]
Ans. (i) Both geometrical (cis-, trans-) isomers for K Cr(H 2O) 2 (C 2O 4 ) 2 can exist. Also, optical
isomers for cis-isomer exist.
Geometrical isomers
OH2 OH2
XO OX XO OH2
Cr Cr
XO OX , XO OX
OH2 XO
Trans Cis
Trans-isomer is optically inactive. On the other hand, cis-isomer is optically active.

OH2 OH
XO OH2 OH2 2 OX
Cr Cr
XO OX XO OX
XO OX
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(ii) Two-optical isomers for CO(en)3 Cl3 exist.

CH2
H2 N CH2 N
CH2 – H2N NH2 N N
Co Co
CH2 – H2N NH2 N N
H2N CH2 N
CH2
Two optical isomers are possible for this structure
N N
N N N N
Co Co
N N N N
N N
®
(iii) CO(NH 3 )5 (NO 2 ) (NO 3 ) 2
A pair of optical isomers
NH3 NH3
O2 N NH3 H3N NO2
Co Co
H3 N NH3 H3N NH3
NH3 NH3
It can also show linkage isomerism

CO(NH 3 )5 (NO 2 ) (NO 3 ) 2 and CO(NH 3 ) 5 (ONO) (NO 3 ) 2
It can also show ionization isomerism
Co(NH 3 )5 (NO 2 ) (NO3 ) 2 and CO(NH 3 )5 (NO 3 ) (NO 3 ) (NO 2 )
(iv) Geometrical (cis-, trans-) isomers of Pt(NH3 ) (H 2O)Cl 2 can exist.
Cl NH3 H3N Cl
Pt Pt
Cl H2O Cl H2O
Cis Trans
Q.4 Give evidence that [Co(NH3)5Cl]SO4 and [Co(NH3)5SO4]Cl are ionization isomers.
Ans. When ionization isomers are dissolved in water, they ionize to give different ions. These ions
then react differently
[CO(NH3)5Cl]SO4 + Ba2+ BaSO4

White precipitate
+
[CO(NH3)5Cl]SO4 + Ag No reaction
[CO(NH3)5SO4]Cl + Ba2+ No reaction
[CO(NH3)5SO4]Cl + Ag+ AgCl
White precipitate
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Q.5 Explain on the basis of valence bond theory that [Ni(CN) 4]2– ion with square planar structure is
diamagnetic and the [NiCl4]2– ion with tetrahedral geometry is paramagnetic.
Ans. Ni is in the +2 oxidation state i.e., in d8 configuration.
d8 configuration :
3d 4s 4p 4d
There are 4 CN– ions. Thus, it can either have a tetrahedral geometry or square planar geometry.
Since CN– ion is a strong field ligand, it causes the pairing of unpaired 3d electrons.
3d 4s 4p 4d
®
It now undergoes dsp2 hybridization. Since all electrons are paired, it is diamagnetic.
In case of [NiCl4]2–, Cl– ion is a weak field ligand. Therefore, it does not lead to the pairing of
unpaired 3d electrons. Therefore, it undergoes sp3 hybridization.
3d 4s 4p 4d
Since there are 2 unpaired electrons in this case, it is paramagnetic in nature.

Q.6 [NiCl4]2– is paramagnetic while [Ni(CO)4] is diamagnetic though both are tetrahedral. Why?
Ans. Though both [NiCl4]2– and [Ni(CO)4] are tetrahedral, their magnetic characters are different. This
is due to a difference in the nature of ligands. Cl– is a weak field ligand and it does not cause the
pairing of unpaired 3d electrons. Hence, [NiCl4]2– is paramagnetic.
Ni+2
3d 4s 4p 4d
In Ni(CO)4, Ni is in the zero oxidation state i.e., it has a configuration of 3d8 4s2.
3d 4s 4p 4d
But CO is a strong field ligand. Therefore, it causes the pairing of unpaired 3d electrons. Also, it
causes the 4s electrons to shift to the 3d orbital, thereby giving rise to sp3 hybridization. Since no
unpaired electrons are present in this case, [Ni(CO)4] is diamagnetic.

Q.7 '[Fe(H2O)6]3+ is strongly paramagnetic whereas [Fe(CN)6]3– is weakly paramagnetic. Explain.
3 3
Ans. In both Fe(H 2O) 6 and Fe(CN)6 , Fe exists in the +3 oxidation state
i.e., in d5 configuration.
d5
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Since CN– is a strong field ligand, it causes the pairing of unpaired electrons. Therefore, there is
only one unpaired electron left in the d-orbital.
Therefore, = n(n 2) = 1(1 2) = 3 = 1.732 BM

On the other hand, H2O is a weak field ligand. Therefore, it cannot cause the pairing of electrons.
This means that the number of unpaired electrons is 5.
Therefore, n(n 2) = 5(5 2) = 35 = 6 BM

3 3
Thus, it is evident that Fe(H 2O) 6 is strongly paramagnetic, while Fe(CN)6 is weakly
paramagnetic.
®
Q.8 Explain [Co(NH3)6]3+ is an inner orbital complex whereas [Ni(NH3)6]2+ is an outer orbital
complex.
Ans. [Co(NH3)6]3+ [Ni(NH3)6]2+

Oxidation state of cobalt = +3 Oxidation state of Ni = +2
Electronic configuration of cobalt = d6 Electronic configuration of Ni = d8
3d 4s 4p 4d 3d 4s 4p 4d
NH3 being a strong field ligand causes the If NH3 causes the pairing, then only one 3d orbital is
2 3
pairing. Therefore, Cobalt can undergo d2sp3 empty. Thus, it cannot undergo d sp hybridization.
hybridisation Therefore, it undergoes sp3d2 hybridization.
3d 4s 4p 4d 3d 4s 4p 4d
d2sp3 sp3d2
Hence, it is an inner orbital complex. Hence, it forms an outer orbital complex.
Q.9 Predict the number of unpaired electrons in the square planar [Pt(CN)4]2– ion.
2
Ans. Pt(CN)6
In this complex, Pt is in the +2 state. It forms a square planar structure. This means that it
undergoes dsp2 hybridization. Now, the electronic configuration of Pt(+2) is 5d8.
3d8
CN– being a strong field ligand causes the pairing of unpaired electrons. Hence, there are no
2
unpaired electrons in Pt(CN) 4 .
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Q.10 The hexaquo manganese(II) ion contains five unpaired electrons, while the hexacyanoion
contains only one unpaired electron. Explain using Crystal Field Theory.
Ans. [Mn(H2O)6]2+ [Mn(CN)6]4–
Mn is in the +2 oxidation state. Mn is in the +2 oxidation state.
The electronic configuration is d5. The electronic configuration is d5.
The crystal field is octahedral. Water is a The crystal field is octahedral. Cyanide is a
weak field ligand. Therefore, the arrangement strong field ligand. Therefore, the arrangement
2 4
of the electrons in Mn(H 2O)6 is t 32g eg2 . of the electrons in Mn(CN)6 is t 52g eg0 .
Q.11 Calculate the overall complex dissociation equilibrium constant for the Cu(NH 3 ) 42 ion, given
that 4 for this complex is 2.1 × 1013.
®
4
Ans. = 2.1 × 1013
The overall complex dissociation equilibrium constant is the reciprocal of the overall stability
constant 4.
1 1
13
= 4.7 × 10–14
4 2.1 10
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EXERCISE-2 NCERT EXERCISE

1. Explain the bonding in coordination compounds in terms of Werner's postulates ?
Ans. Werner's postulates explain the bonding in coordination compounds as follows :
(i) A metal exhibits two types of valencies namely, primary and secondary valencies. Primary
valencies are satisfied by negative ions while secondary valencies are satisfied by both
negative and neutral ions.
(ii) A metal ion has a definite number of secondary valencies around the central atom. Also,
these valencies project in a specific direction in the space assigned to the definite geometry
of the coordination compound.
(iii) Primary valencies are usually ionizable, while secondary valencies are non-ionizable.
2. FeSO4 solution mixed with (NH4)2 SO4 solutions in 1 : 1 molar ratio gives the test of Fe2+ ion but
CuSO4 solution mixed with aqueous ammonia in 1 : 4 molar ratio does not give the test of Cu2+
ion. Explain why ?
®
Ans. (NH 4 ) 2 SO 4 FeSO 4 6H 2 O FeSO 4 .(NH 4 ) 2 SO 4 .6H 2 O
Mohr'sSalt
CuSO4 4NH 3 5H 2O [Cu(NH3 ) 4 ]SO 4 .5H 2O

Tetraammin ocopper( II)sulphate
Both the compounds i.e., FeSO4. (NH4)2 SO4. 6H2O and [Cu(NH3)4] SO4. 5H2O fall under the
category of addition compounds with only one major difference i.e., the former is an example of
a double salt, while the latter is a coordination compound.
3. Explain with two examples each of the following: coordination entity, ligand, coordination
number, coordination polyhedron, homoleptic and heteroleptic.
Ans. (i) Coordination entity : A coordination entity is an electrically charged radical or species
carrying a positive or negative charge. In a coordination entity, the central atom or ion is
surrounded by a suitable number of neutral molecules or negative ions (called ligands). For
example :
2 3
Ni(NH 3 )6 , Fe(NH3 )6 cationic complex
2
PtCl 4 , Ag(CN)2 anionic complex
Ni CO 4
, Co NH3 4 Cl2 neutral complex
(ii) Ligands : The neutral molecules or negatively charged ions that surround the metal atom
in a coordination entity or a coordinal complex are known as ligands. For example Cl–,
H2O, H2N CH2CH2NH2 etc.
(iii) Coordination number : The total number of ligands (either neutral molecules or negative
ions) that get attached to the central metal atom in the coordination sphere is called the
coordination number of the central metal atom. It is also referred to as its ligancy.
For example :
(a) In the complex, K2[PtCl6], there as six chloride ions attached to Pt in the coordinate
sphere. Therefore, the coordination number of Pt is 6.
(b) Similarly, in the complex [Ni(NH3)4]Cl2, the coordination number of the central atom
(Ni) is 4.
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(iv) Coordination polyhedron : Coordination polyhedrons about the central atom can be
defined as the spatial arrangement of the ligands that are directly attached to the central
metal ion in the coordination sphere. For example :
L
L L
M L M
(a) (b) L
L L
Square planar L Tetrahedral
(v) Homoleptic complexes : These are those complexes in which the metal ion is bound to
only one kind of a donor group.
3 2
For e.g. Co(NH3 )6 , PtCl 4 etc.
®
(vi) Heteroleptic complexes : Heteroleptic complexes are those complexes where the central
metal ion is bound to more than one type of a donor group.
2
For e.g. Co(NH3 ) 4 Cl 2 , Co(NH3 )5 Cl
4. What is meant by unidentate, didentate and ambidentate ligands ? Give two examples for each.
Ans. A ligand may contain one or more unshared pairs of electrons which are called the donor sites of
ligands. Now, depending on the number of these donor sites, ligands can be classified as follows :
(a) Unidenatate ligands : Ligands with only one donor sites are called unidentate ligands. For
e.g., N H3 ,Cl — etc.

(b) Didentate ligands : Ligands that have two donor sites are called bidentate ligands. For e.g.,
(i) Ethane-1, 2-diamine (ii) Oxalate ion
H2N—CH2 COO—
2–
(C2O ) or
H2N—CH2 4
COO
—
(c) Ambidentate ligands : Ligands that can attach themseleves to the central metal atom
through two different atoms are called ambidentate ligands. For example :
O
M—N Nitro group
(i)
O
(The donor atom is N)
M—O—N = O Nitrito group
(The donor atom is oxygen)

M—SCN Thiocyanato
(ii)
(The donor atom is S)
M—NCS Isothiocyanato
(The donor atom is N)

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5. Specify the oxidation numbers of the metals in the following coordination entities :
(i) [Co(H2O)(CN)(en)2]2+ (ii) [CoBr2(en)2]+
(iii) [PtCl4]2– (iv) K3[Fe(CN)6]
(v) [Cr(NH3)3Cl3]
Ans. (i) [Co(H2O)(CN)(en)2]2+
Let the oxidation number of Co be x.
The charge on the complex is +2.
2+
Co (H2O) (CN) (en)2
x + 0 + (–1) + 2(0) = +2
x – 1 = +2
®
x = +3
(ii) [PtCl4]2–
Let the oxidation number of Pt be x.
The charge on the complex is –2.
2—
Pt (Cl)4
x + 4(–1) = –2
x = +2
+
Co (Br)2 (en)2
(iii)
x + 2(–1) + 2(0) = +1
x – 2= +1
x =+3
(iv) K3[Fe(CN)6]
3–
i.e., Fe (CN)6
x + 6(–1) = –3
x = +3
Cr (NH 3)3 Cl3

(v)
x + 3(0) + 3(-1) = 0
x–3=0
x = +3
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6. Using IUPAC norms write the formulas for the following :

(i) Tetrahydroxozincate (II) (ii) Potassium tetrachloridopalladate (II)
(iii) Diamminedichloridoplatinum (II) (iv) Potassium tetracyanonickelate (II)
(v) Pentaamminenitrito-O-cobalt (III) (vi) Hexaamminecobalt (III) sulphate
(vii) Potassium tri(oxalato)chromate (III) (viii) Hexaammineplatinum (IV)
(ix) Tetrabromidocuprate (II) (x) Pentaamminenitrito-N-cobalt (III)
Ans. (i) [Zn(OH)4]2– (ii) K2[PdCl4]
(iii) [Pt(NH3)2Cl2] (iv) K2[Ni(CN)4]
2+
(v) [Co(ONO) (NH3)5] (vi) [Co(NH3)6]2 (SO4)3
(vii) K3[Cr(C2O4)3] (viii) [Pt(NH3)6]4+
(ix) [Cu(Br)4]2– (x) [Co[NO2)(NH3)5]2+
7. Using IUPAC norms write the systematic names of the following :
®
(i) [Co(NH3)6]Cl3 (ii) [Pt(NH3)2Cl(NH2CH3)]Cl
3+
(iii) [Ti(H2O)6] (iv) [Co(NH3)4Cl(NO2)]Cl
2+
(v) [Mn(H2O)6] (vi) [NiCl4]2–
(vii) [Ni(NH3)6]Cl2 (viii) [Co(en)3]3+
(ix) [Ni(CO)4]
Ans. (i) Hexaamminecobalt (III) chloride
(ii) Diamminechlorido (methylamine) platinum (II) chloride
(iii) Hexaaquatitanium (III) ion
(iv) Tetraamminechloridonitrito-N-Cobalt (III) chloride
(v) Hexaaquamanganese (II) ion
(vi) Tetrachloridonickelate (II) ion
(vii) Hexaamminenickel (II) chloride
(viii) Tris (ethane-1, 2-diammine) cobalt (III) ion
(ix) Tetracarbonylnickel (0)
8. List various types of isomerism possible for coordination compounds, giving an example of each.
Ans. Isomerism in coordination compounds
Stereoisomerism Structural isomersim
Geometrical Optical Solvate Linkage Coordination Ionization

isomerism isomerism isomerism isomerism isomerism isomerism
(a) Geometrical isomerism : This type of isomerism is common in heteroleptic complexes. It

arises due to the different possible geometric arrangements of the ligands. For example :
Cl NH3 Cl NH3
Pt Pt
Cl NH3 NH3 Cl
Cis-isomer Trans-isomer
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(b) Optical isomerism : This type of isomerism arises in chiral molecules. Isomers are mirror
images of each other and are non-superimposable.
en en
en Co Co en
en en
3+
[Co(en)3] Mirror [Co(en)3]3+
(dextro) (Laevo)
(c) Linkage isomerism : This type of isomerism is found in complexes that contain
ambidentate ligands.
For example : [Co(NH3)5(NO2)]Cl2 and [Co(NH3)5(ONO)Cl2
®
Yellow form Red form
(d) Coordination isomerism : This type of isomerism arises when the ligands are
interchanged between cationic and anionic entities of different metal ions present in the
complex. For example [Co(NH3)6] [Cr(CN)6] and [Cr(NH3)6] [Co(CN)6]
(e) Ionization isomerism : This type of isomerism arises when a counter ion replaces a ligand
within the coordination sphere. For example
[Co(NH3)5 SO4] Br and [Co(NH3)5Br] SO4
(f) Solvate isomerism : Solvate isomers differ by whether or not the solvent molecule is
directly bonded to the metal ion or merely present as a free solvent molecule in the crystal
lattice.
[Cr(H2O)6]Cl3, [Cr(H2O)5Cl]Cl2. H2O, [Cr(H2O)4Cl2]Cl. 2H2O
Violet Blue-green Dark green
9. How many geometrical isomers are possible in the following coordination entities ?
(i) [Cr(C2O4)3]3+ (ii) [Co(NH3)3Cl3]
Ans. (i) For [Cr(C2O4)3]3–, no geometrical isomer is possible as it is a bidentate ligand.
O
OX O
XO
O
XO Cr OX
O
O
XO O
OX
(ii) [Co(NH3)3Cl3], Two geometrical isomers are possible.

NH3 H3N NH3
Cl NH3 Cl
Co Co
Cl NH3 Cl Cl
Cl NH3
Facial Meridional
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10. Draw the structure of optical isomers of :

(i) [Cr(C2O4)3]3– (ii) [PtCl2(en)2]2+ (iii) [Cr(NH3)2Cl2(en)]+
Ans. (i) [Cr(C2O4)3]3–
en en
en Co Co en
en en
3–
[Cr(OX)3] Mirror [Cr(OX)3]3–
(dextro) (Laevo)
(ii) [PtCl2(en)2]2+
Cl Cl
Cl
en en
®
Pt Pt
en en
Mirror
+
(iii) [Cr(NH3)2Cl2(en)]
en en
H3N NH3
Cr Cr
H3N Cl Cl NH3
Cl Cl
Mirror
11. Draw all the isomers (geometrical and optical) of :
(i) [CoCl2(en)2]+ (ii) [Co(NH3)Cl(en)2]2+ (iii) [Co(NH3)2Cl2 (en)]+
Ans. (i) [CoCl2(en)2]+
Cl Cl
en Co en Co en
en
Cl Cl
Mirror
Trans [CoCl2(en)2]+ isomer-optically inactive
(Superimposable mirror images)
Cl Cl
Cl Cl
en Co Co en
en en
Mirror
+
Cis [CoCl2(en)2] isomer-optically active
(non-superimposable mirror images)
In total, three isomers are possible.

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(ii) [Co(NH3)Cl(en)2]2+
Cl Cl
NH3
en Co
en en Co
NH3 en
Trans Cis
Cl Cl
NH3 H3N
en Co Co en
en en
Cis Mirror
®
Trans - isomers are optically inactive.
Cis - isomers are optically active.
(iii) [Co(NH3)2Cl2(en)]+
Cl Cl
Cl Cl
en Co Co en
NH3 NH3
NH3 NH3
Mirror
12. Write all the geometrical isomers of [Pt(NH3)(Br)(Cl)(py)] and how many of these will exhibit
optical isomers ?
Ans. [Pt(NH3)(Br)(Cl)(py)]
H3N Cl H3N Br H3N Cl
Pt Pt Pt
Py Br Py Cl Br Py
From the above isomers, none will exhibit optical isomers. Tetrahedral complexes rarely show
optical isomerization. They do so only in the presence of unsymmetrical chelating agents.
13. Aqueous copper sulphate solution (blue in colour) gives :
(i) A green precipitate with aqueous potassium fluoride, and
(ii) A bright green solution with aqueous potassium chloride
Explain these experimental results.

Ans. Aqueous CuSO4 exists as [Cu(H2O)4]SO4. It is blue in colour due to the presence of
[Cu(H2O)4]2+ ions.
(i) When KF is added.
2 2
Cu H 2 O 4 4F Cu F 4
4H 2 O
(Green)
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(ii) When KCl is added :

2 2
Cu H 2 O 4 4Cl CuCl 4 4H 2 O
(bright green)
In both these cases, the weak field ligand water is replaced by the F— and Cl— ions.
14. What is the coordination entity formed when excess of aqueous KCN is added to an aqueous
solution of copper sulphate? Why is it that no precipitate of copper sulphide is obtained when
H2S (g) is passed through this solution?
Ans. CuSO4(aq) 4KCN(aq) K 2 Cu(CN)4 (aq)
K 2SO4(aq)
2 2
i.e., Cu(H 2O)4 4CN Cu(CN) 4 4H 2O
Thus, the coordination entity formed in the process is K2[Cu(CN)4]. It is a very stable complex,
which does not ionize to give Cu2+ ions when added to water. Hence, Cu2+ ions are not
®
precipitated when H2S(g) is passed through the solution.
15. Discusss the nature of bonding in the following coordination entities on the basis of valence bond
theory :
(i) [Fe(CN)6]4– (ii) [FeF6]3– (iii) [Co(C2O4)3]3– (iv) [CoF6]3–
Ans. (i) [Fe(CN)6]4–
In the above coordination complex, iron exists in the +2 oxidation state.
Fe2+ : Electronic configuration is 3d6
Orbitals of Fe2+ ion :
3d 4s 4p
As CN— ion is a strong field ligand, it causes the pairing of the unpaired 3d electrons.
3d 4s 4p
Since there are six ligands around the central metal ion, the most feasible hybridization is
d2sp3.
d2sp3 hybridized orbitals of Fe2+ are :
3d 4s 4p
d sp2 3
6 electron pairs from CN ions occupy the six hybrid d2sp3 orbitals.
–
Then,
3d 4s 4p
6 pairs of electrons from 6CN ions—
Hence, the geometry of the complex is octahedral and the complex is diamagnetic
(as there are no unpaired electrons).
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(ii) [FeF6]3–
In this complex, the oxidation state of Fe is +3.
Orbitals of Fe+3 ion :
3d 4s 4p 4d
There are 6 F ions. Thus, it will undergo d sp or sp d hybridization. As F– is a weak field
– 2 3 3 2
ligand, it does not cause the pairing of the electrons in the 3d orbitals. Hence, the most
feasible hybridization is sp3d2.
sp3d2 hybridized orbitals of Fe3+ it are :
3d 4s 4p 4d
sp3d2
®
3d 4s 4p 4d
sp3d2
6 electron pairs from F—ions
Hence, the geometry of the complex is found to be octahedral.

(iii) [Co(C2O4)3]3–
Cobalt exists in the +3 oxidation state in the given complex.
Orbitals of Co3+ ion :
3d 4s 4p 4d
Oxalate ion is a weak field ligand. Therefore, it cannot cause the pairing of the 3d orbital
electrons. As there are 6 ligands, hybridization has to be sp3d2.
sp3d2 hybridized orbitals of Co3+.
sp3d2
The 6 electron pairs from the 3 oxalate ions (oxalate anion is a bidentate ligand) occupy
these sp3d2 orbitals.
6 electron pairs from 3 oxalate ions
Hence, the geometry of the complex is found to be octahedral.

(iv) [CoF6]3–
Cobalt exists in the +3 oxidation state.
Orbitals of Co3+ ion :
3d 4s 4p 4d
Again, fluoride ion is a weak field ligand. It cannot cause the pairing of the 3d electrons.
As a result, the Co3+ ion will undergo sp3d2 hybridization.
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sp3d2 hybridized orbitals of Co3+ ion are :
3d 4s 4p 4d
sp d
3 2
3d 4s 4p 4d
sp3d2
6 electron pairs from F— ions
Hence, the geometry of the complex is octahedral and paramagnetic.

16. Draw figure to show the splitting of d obitals in an octahedral crystal field.
Ans. Energy dx2– y2,dz2
z eg
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y +3/5
Barycentre
–2/5
x
Average energy t2g
of the d orbitals dxy dyz dxz
in a spherical field
Splitting of the d
Metal orbitals in a
d orbitals octahedral crystal field
dx2–y2–dz2, dxydyzdxz
17. What is spectrochemical series ? Explain the difference between a weak field and a strong field
ligand.
Ans. A spectrochemical series is the arrangement of common ligands in the increasing order of their
crystal - field splitting energy (CFSE) values. The ligands present on the R.H.S of the series are
strong field ligands while that on the L.H.S are weak field ligands. Also, strong field ligands
cause higher splitting in the d orbitals that weak field ligands.
I–< Br– <S2– <SCN– <Cl– <N3– <OH– <C2O42– <~H2O < NCS– <edta4– < NH3 < en– <CN– < CO
18. What is crystal field splitting energy ? How does the magnitude of o decide the actual
configuration of d-orbitals in a coordination entity ?
Ans. The degenerate d-orbitals (in a spherical field environment) split into two levels i.e., eg and t2g in
the presence of ligands. The splitting of the degenerate levels due to the presence of ligands is
called the crystal – field splitting while the energy difference between the two levels (e g and t2g)
is called the crystal - field splitting energy. It is denoted by 0.
After the orbitals have split, the filling of the electrons takes place. After 1 electron (each) has
been filled in the three t2g orbitals, the filling of the fourth electron takes place in two ways. It can
enter the eg orbitals (giving rise to t2g3 eg1 like electron configuration) or the pairing of the
electrons can take place in the t2g orbitals (giving rise to t2g4 eg0 like electronic configuration). If
the 0 value of a ligand is less than the pairing energy (P), then the electrons enter the eg orbital.
On the other hand, if the 0 value of a ligand is more than the pairing energy (P), then the
electrons enter the t2g orbital.
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19. [Cr(NH3)6]3+ is paramagnetic while [Ni(CN)4]2– is diamagnetic. Explain why ?
Ans. In [Cr(NH3)6]3+, Cr is in the +3 oxidation state i.e., d3 configuration. Since there are three
unparied electrons in 3d– orbitals
Cr3+
3d 4s 4p 4d
d2sp3
Therefore, it undergoes d2sp3 hybridization and the electrons in the 3d orbitals remain unpaired.
Hence, it is paramagnetic in nature.
In [Ni(CN)4]2– Ni exists in the +2 oxidation state i.e., d8 configuration.
Ni2+
3d 4s 4p
CN is a strong field ligand. It cause the pairing of the 3d orbital electrons. Then, Ni2+ undergoes
–
dsp2 hybridization.
®
3d 4s 4p
dsp2
As there are no unpaired electrons, it is diamagnetic.
20. A solution of [Ni(H2O)6]2+ is green but a solution of [Ni(CN)4]2– is colourless. Explain.
Ans. In [Ni(H2O)6]2+, H2 O is a weak field ligand. Therefore, there are unpaired elecrons in Ni2+. In
this complex, the 3d electrons from the lower energy level can be excited to the higher energy
level i.e., the possibility of d-d transition is present. Hence, [Ni(H2O)6]2+ is coloured.
In [Ni(CN)4]2– the electrons are all paired as CN– is a strong field ligand. Therefore, d-d
transition is not possible is [Ni(CN)4]2–. Hence, it is colourless.
21. [Fe(CN)6]4– and [Fe(H2O)6]2+ are of different colours in dilute solutions. Why ?
Ans. The colour of a particular coordination compound depends on the magnitude of the crystal-field
splitting energy, . This CFSE in turn depends on the nature of the ligand. In case of [Fe(CN)6]4–
and [Fe(H2O)6]2+, the colour differs because there is a difference in the CFSE. Now CN– is a
strong field ligand having a higher CFSE value of compound to the CFSE value of water. This
means that the absorption of energy for the intra d-d transition also differs. Hence the transmitted
colour also differs.
22. Discuss the nature of bonding in metal carbonyls.
Ans. The metal -carbon bonds in metals carbonyls have both and characters. A bond is formed
when the carbonyl carbon donates a lone pair of electrons to the vacant orbital of the metal. A
bond is formed by the donation of a pair of electrons from the filled metal d orbital into the
vacent anti-bonding orbital (also known as back bonding of the carbonyl group). The bond
strengthens the bond and vica - versa. Thus, a synergic effect is created due to this metal -
ligand bonding. This synergic effect strengthens the bond between CO and the metal.
M C O
Synergic bonding in metal carbonyls

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23. Give the oxidation state, d- orbital occupation and coordination number of the central metal ion
in the following complexes :
(i) K3[Co(C2O4)3] (ii) cis-[Cr(en)2Cl2]Cl
(iii) (NH4)2[CoF4] (iv) [Mn(H2O)6]SO4
Ans. (i) K3[Co(C2O4)3]
The central metal ion is Co3+.
Its coordination number is 6.
The oxidation state can be given as:
x – 6 = –3
x = +3
The d orbitals occupation for Co3+ is t 62g e0g .
®
(ii) cis-[Cr(en)2Cl2]Cl
The central metal ion is Cr3+.
The coordination number is 6.
The oxidation state can be given as :
x + 2(0) + 2(–1) = +1
x – 2 = +1
x = +3
The d orbitals occupation for Cr3+ is t 32g .
(iii) (NH4)2[CoF4]
The central metal ion is Co2+.
x – 4 = –2
x = +2
The d orbitals occupation for Co2+ is eg4 t2g3.
(iv) [Mn(H2O)6]SO4
The central metal ion is Mn2+.

x + 0 = +2
x = +2
The d orbitals occupation for Mn2+ is t 32g e2g .
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24. Write down the IUPAC name for each of the following complexes and indicate the oxidation
state, electronic configuration and coordination number. Also give stereochemistry and magnetic
moment of the complex :
(i) K[Cr(H2O)2(C2O4)2]. 3H2O (ii) [Co(NH3)5Cl]Cl2
(iii) CrCl3(py)3 (iv) Cs[FeCl4]
(v) K4[Mn(CN)6]
Ans. (i) K[Cr (H2O)2 (C2O4)2]. 3H2O
IUPAC Name: Potassium diaquadioxalatochromate (III) trihydrate.
Oxidation state of chromium = +3
Electronic configuration : 3d3
®
Coordination number = 6
Shape : octahedral
Stereochemistry :
OH2 OH2
XO
O OX
O XO
O OH2
Cr Cr
O
XO O
OX O
XO OX
O
OH2 OX
Trans Cis
OH2 OH2 OH2 OH2

XO
O OX
O XO
O OX
O XO
O OH2 H2O OX
O
Cr Cr Cr Cr
O O
OX O O
OX OX
XO XO XO
O O XO
O OX
O
OH2 OH2 O
XO OX
O
Trans optically inactive Cis optically active
Magnetic moment, n n 2
= 3 3 2 = 5 ~ 4BM
(ii) [Co(NH3)5Cl]Cl2
IUPAC name : Pentaamminechloridocobalt (III) chloride
Oxidation state of Co = +3
Shape : octahedral.
Electronic configuration : d6: t 62g .
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Stereo chemistry :
OH2 OH2
XO
O OH2 H2O O
OX
Cr Cr
O
XO O
OX O
XO O
OX
XO
O OX
O
Cis optically active
Magnetic Moment = 0
(iii) CrCl3(py)3
IUPAC name : Trichloridotripyridinechromium (III)
®
Oxidation state of chromium = +3
Electronic configuration for: d3 t2g

3
Shape : octahedral.
Stereochemistry :
Cl Cl
Py Cl Py Cl
Cr Cr
Py Cl Py Py
Py Cl
Facial isomer Meriodional isomer
Both isomers are optically active. Therefore, a total of 4 isomers exist.
Magnetic moment, n(n 2) = 3(3 2) = 15 ~ 4BM
(iv) Cs[FeCl4]
IUPAC name: Caesium tetrachloroferrate (III)
Oxidation state of Fe =+3
Electronic configuration d5: e 2g t 23 g
Shape : tetrahedral
Stereochemistry : optically inactive
Magnetic moment :
n(n 2) = 5(5 2) = 35 ~ 6BM

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(v) K4[Mn(CN)6]
IUPAC Name : Potassium hexacyanomanganate (II)
Oxidation state of manganese = +2
Electronic configuration :d5: t 52g
Shape : octahedral
Streochemistry : optically inactive
Magnetic moment, n(n 2) = 1(1 2) = 3 = 1.732 BM

25. What is meant by stability of a coordination compound in solution? State the factors which
govern stability of complexes.
®
Ans. The stability of a complex in a solution refers to the degree of association between the two
species involved in a state of equilibrium. Stability can be expressed quantitatively in terms of
stability constant or formation constant.
M + 3L ML3
[ML 3 ]
Stability constant, =
[M][L]3
For this reaction, the greater the value of the stability constant, the greater is the proportion of
ML3 in the solution.
Stability can be of two types :
(a) Thermodynamic stability : The extent to which the complex will be formed or will be
transformed into another species at the point of equilibrium is determined by
thermodynamic stability.
(b) Kinetic stability : This helps is determining the speed with which the transformation will
occur to attain the state of equilibrium.
26. What is meant by the chelate effect ? Give an example.
Ans. When a ligand attaches to the metal ion in a manner that forms a ring, then the metal-ligand
association is found to be more stable. In other words, we can say that complex containing
chelate rings are more stable than complexes without rings. This is known as the chelate effect.
For example : en
en Ni
2 2
Ni (aq ) 6NH 3(aq ) Ni(NH 3 )6 (aq )
log = 7.99
en
2
Ni 2 ( aq ) 3en ( aq ) Ni(en) 3 ( aq )
log = 18.1 (more stable)
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27. Discuss briefly giving an example in each case the role of coordination compounds in :
(i) biological system
(ii) medicinal chemistry
(iii) analytical chemistry
(iv) extraction/metallurgy of metals
Ans. (i) Role of coordination compounds in biological system : We know that photosynthesis is
made possible by the presence of the chlorophyll pigment. This pigment is a coordination
compound of magnesium.
(ii) Role of coordination compounds in medicinal chemistry : Certain coordination
compounds of platinum (for example, cis-platin) are used for inhibiting the growth of
tumours.
®
(iii) Role of coordination compounds in analytical chemistry : During salt analysis, a
number of basic radicals are detected with the help of the colour changes they exhibit with
different reagents.
(iv) Role of coordination compounds in extraction or metallurgy of metals : From
[Au(CN)2]+ solution, gold is extracted by the addition of zinc metal.
28. How many ions are produced from the complex [Co(NH3)6]Cl2 in solution ?
(i) 6 (ii) 4 (iii) 3 (iv) 2
Ans. (iii) The given complex can be written as [Co(NH3)6]Cl2
Thus, [Co(NH3)6]2+ along with two Cl– ions are produced.
29. Amongst the following ions which one has the highest magnetic moment value ?
(i) [Cr(H2O6)]3+ (ii) [Fe(H2O)6]2+ (iii) [Zn(H2O)6]2+
Ans. (i) No. of unpaired electrons in [Cr(H2O6)]3+ = 3
Then, = n(n+2) = 3(3 2) = 15 ~ 4BM
(ii) No. of unpaired electrons in [Fe(H2O)6]2+ = 4
Then, 4(4 2) = 24 ~ 5BM
(iii) No. of unpaired electrons in [Zn(H2O)6]2+ = 0

Hence, [Fe(H2O)6]2+ has the highest magnetic moment value.

30. The oxidation number of cobalt in K[Co(CO)4] is
(i) +1 (ii) +3 (iii) –1 (iv) –3
Ans. We know that CO is a neutral ligand and K carries a charge of +1.
Therefore, the complex can be written as K+[Co(CO)4]–. Therefore, the oxidation number of Co
in the given complex is –1. Hence, option (iii) is correct.
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ALLEN
EXERCISE-3 EXEMPLAR
1. The colour of the coordination compounds depends on the crystal field splitting. What will be the
correct order of absorption of wavelength of light in the visible region, for the complexes,
[Co(NH3)6]3+, [Co(CN)6]3–, [Co(H2O)6]3+
(a) [Co(CN)6]3– > [Co(NH3)6]3+ > [Co(H2O)6]3+
(b) [Co(NH3)6]3+ > [Co(H2O)6]3+ > [Co(CN)6]3–
(c) [Co(H2O)6]3+ > [Co(NH3)6]3+ > [Co(CN)6]3–
(d) [Co(CN)6]3– > [Co(NH3)6]3+ < [Co(H2O)6]3+
Ans. (c)
2. The correct IUPAC name of [Pt(NH3)2Cl2] is :
(a) Diamminedichloridoplatinum (II) (b) Diamminedichloridoplatinum (IV)
®
(c) Diamminedichloridoplatinum (0) (d) Dichloridodiammineplatinum (IV)
Ans. (a)
3. The stabilisation of coordination compounds due to chelation is called the chelate effect. Which
of the following is the most stable complex species ?
(a) [Fe(CO)5] (b) [Fe(CN)6]3– (c) [Fe(C2O4)3]3– (d) [Fe(H2O)6]3+
Ans. (c)
4. Indicate the complex ion which shows geometrical isomerism :
(a) [Cr(H2O)4 Cl2]+ (b) [Pt(NH3)3Cl]
(c) [Co(NH3)6]3+ (d) [Co(CN)5(NC)]3–
Ans. (a)
5. Due to the presence of ambidentate ligands coordination compounds show isomerism. Palladium
complexes of the type [Pd(C6H5)2(SCN)2] and [Pd(C6H5)2(NCS)2] are :
(a) linkage isomers (b) coordination isomers
(c) ionisation isomers (d) geometrical isomers
Ans. (a)
6. The compounds [Co(SO4) (NH3)5]Br and [Co(SO4) (NH3)5]Cl represent :
(a) linkage isomerism (b) ionisation isomerism
(c) coordination isomerism (d) no isomerism
Ans. (b)
7. What kind of isomerism exists between [Cr(H2O)6]Cl3 (violet) and [Cr(H2O)5Cl]Cl2.H2O
(greyish-green) ?
(a) Linkage isomerism (b) Solvate isomerism
(c) Ionisation isomerism (d) Coordination isomerism
Ans. (b)
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8. IUPAC name of [Pt(NH3)2 Cl(NO2)] is :
(a) Platinum diaminechloronitrite
(b) Chloronitrito-N-ammineplatinum (II)
(c) Diamminechloridonitrito-N-platinum (II)
(d) Diamminechloronitrito-N-platinate (II)
Ans. (c)
(SHORT ANSWER TYPE QUESTIONS)
9. Arrange the following complexes in the increasing order of conductivity of their solution :
[Co(NH3)3Cl3], [Co(NH3)4Cl2]Cl, [Co(NH3)6]Cl3, [Cr(NH3)5Cl]Cl2
Ans. Ions or molecules present outside the coordination sphere are ionisable. A complex which gives
more ions on dissolution, is more conducting.
®
[Co(NH3)3Cl3] < [Co(NH3)4Cl2]Cl < [Cr(NH3)5Cl]Cl2 < [Co(NH3)6]Cl3
(1 ion) (2 ions) (3 ions) (4 ions)
Here, number of ions increases and conductivity increases.
10. A complex of the type [M(AA)2X2]n+ is known to be optically active. What does this indicate
about the structure of the complex ? Give one example of such complex.
Ans. An optically active complex of the type [M(AA)2X2]n+ indicates cis-octahedral structure.
e.g., cis-[Pt(en)2Cl2]2+ or cis-[Cr(en)2Cl2]+ because its mirror image isomers are
non-superimposable.
2+ 2+
en en
en en
Pt Pt
Cl Cl
Cl Cl
Non-superimposable isomers of [Pt(en)2Cl2]2+

Non-superimposable isomers of [Pt(en)2Cl2]2+.
11. Give the electronic configuration of the following complexes on the basis of crystal field splitting
theory. [CoF6]3–, [Fe(CN)6]4– and [Cu(NH3)6]2+
Ans. According to spectrochemical series, ligands can be arranged in a series in the order of increasing
field strength i.e., F– < NH3 < CN–.
Hence, CN– and NH3 being strong field ligand pair up the t2g electrons before filling eg set.
[CoF6]3– ; Co3+ = (d6) t 42g e g2
eg
Degenerate t2g
d-orbital
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Fe(CN)46 , Fe2 (d 6 )t 62q e 0g
eg
Degenerate t2g
d-orbital
2
Cu(NH 3 )6 ,Cu 2 (d 9 ) t eg
6
e3g
eg
Degenerate t2g
®
d-orbital
12. Explain why [Fe(H2O)6]3+ has magnetic moment value of 5.92 BM whereas [Fe(CN)6]3– has a
value of only 1.74 BM ?
Ans. As we know, m n(n 2) BM
where, m = magnetic moment

n = number of unpaired electrons
It m = 1.74 i.e., n = 1
and m = 5.92 i.e., n = 5
[Fe(CN)6] involves d2sp3 hybridisation with one unpaired electron (as shown by its magnetic
3–
moment 1.74 BM) and [Fe(H2O)6]3+ involves sp3d2 hybridisation with the unpaired electrons
(because magnetic moment equal to 5.92 BM).
CN– is stronger ligand than H2O according to spectrochemical series, 0 > P for CN– hence,
fourth electron will pair itself. Whereas for water pairing will not happen for [Fe(CN)6]3– the
electronic configuration of Fe3+ is
× × × × × ×
d2sp3 hybridisation
One unpaired electron (n = 1)

For [Fe(H2O)6]3+ the electronic configuration of Fe3+ is
× × × × × × × × ×
sp3d2 hybridisation
Five unpaired electron (n = 5)

Hence, [Fe(CN)6]3– and [Fe(H2O)6]3+ are inner orbital and outer orbital complex respectively.
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13. Arrange following complex ions is increasing order of crystal field splitting energy ( 0).
[Cr(Cl)6]3–, [Cr(CN)6]3–, [Cr(NH3)6]3+
Ans. CFSE is higher when the complex contains strong field ligand. Thus, crystal field splitting energy
increases in the order.
[Cr(Cl)6]3– < [Cr(NH3)6]3+ < [Cr(CN)6]3–
Because according to spectrochemical series the order of field strength is
Cl– < NH3 < CN–
14. Why do compounds having similar geometry have different magnetic moment ?
Ans. It is due to the presence of weak and strong field ligands in complexes. If CFSE is high, the
complex will show low value of magnetic moment and vice-versa. e.g., [CoF6]3– and
[Co(NH3]6]3+, the former is paramagnetic, and the latter is diamagnetic because F– is a weak field
ligand and NH3 is a strong field ligand while both have similar geometry.
]3– ]3+
®
F NH3
F F NH3 NH3
Co and Co
F F NH3 NH3
F NH3
15. CuSO4.5H2O is blue in colour while CuSO4 is colourless, Why ?
Ans. In CuSO4.5H2O water acts as ligand and causes crystal field splitting. Hence d-d transition is
possible thus CuSO4.5H2O is coloured. In the anhydrous CuSO4 due to the absence of water
(ligand), crystal field splitting is not possible and hence, it is colourless.
(MATCHING THE COLUMNS)
16. Match the complex ions given in Column I with the colours given in Column II and assign the
correct code.
Column-I Column-II
(Complex ion) (Colour)
(A) [Co(NH3)6]3+ (1) Violet
3+
(B) [Ti(H2O)6] (2) Green
2+
(C) [Ni(H2O)6] (3) Pale blue
(D) [Ni(H2O)4(en)]2+ (aq) (4) Yellowish orange
Ans. A-4, B-3, C-2, D-1
17. Match the coordination compounds given in Column I with the central metal atoms given in
Column II and assign the correct code.
Column-I Column-II
(Coordination Compound) (Central metal atom)
(A) Chlorophyll (1) Rhodium
(B) Blood pigment (2) Cobalt
(C) Wilkinson catalyst (3) Magnesium
(D) Vitamin B12 (4) Iron
Ans. A-3, B-4, C-1, D-2
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ALLEN
18. Match the complex ions given in Column I with the hybridisation and number of unpaired
electrons given in Column II and assign the correct code.
Column-I Column-II
(Complex ion) (Hybridisation,
number of unpaired
electrons)
(A) [Cr(H2O)6]3+ (1) dsp2, 1
(B) [Co(CN)4]2– (2) sp3d2, 5
(C) [Ni(NH3)6]2+ (3) d2sp3, 3
®
(D) [MnF6]4– (4) sp3d2, 2
Ans. A-3, B-1, C-4, D-2

19. Match the complex species given in Column I with the possible isomerism given in Column II
and assign the correct code.
Column-I Column-II
(Complex species) (Isomerism)
(A) [Co(NH3)4Cl2]+ (1) Optical
(B) cis-[Co(en)2Cl2]+ (2) Ionisation
(C) [Co(NH3)5(NO2)]Cl2 (3) Coordination
(D) [Co(NH3)6][Cr(CN)6] (4) Geometrical
Ans. A-4, B-1, C-2, D-3

20. Match the compounds given in Column-I with the oxidation state of cobalt present in it
(given in column II) and assign the correct code :
Column-I Column-II
(Compound) (Oxidation state of Co)
(A) [Co(NCS)(NH3)5](SO3) (1) +4

(B) [Co(NH3)4Cl2]SO4 (2) 0
(C) Na4[Co(S2O3)3] (3) +2
(D) [Co2(CO)8] (4) +3
Ans. A-4, B-1, C-3, D-2

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(ASSERTION AND REASON TYPE)
Note: In the following questions a statement of assertion followed by a statement of reason is given.
Choose the correct answer out of the following choices.
(a) Both (A) and (R) correct and (R) is correct explanation of (A).
(b) Both (A) and (R) correct and (R) is not correct explanation of (A).
(c) (A) is correct but (R) is wrong.
(d) (A) Assertion is wrong but (R) reason is correct.
21. Assertion (A) : Toxic metal ions are removed by the chelating ligands.
Reason (R) : Chelate complexes tend to be more stable.
Ans. (a)
22. Assertion (A) : [Cr(H2O6)]Cl2 and [Fe(H2O)6]Cl2 are reducing in nature.
®
Reason (R) : Unpaired electrons are present in their d-orbitals.
Ans. (b)
23. Assertion (A) : Linkage isomerism arises in coordination compounds containing ambidentate
ligand.
Reason (R) : Ambidentate ligand has two different donor atoms.
Ans. (a)
24. Assertion (A) : Complexes of MX6 and MX5 L type (X and L are unidentate) do not show
geometrical isomerism.
Reason (R) : Geometrical isomerism is not shown by complexes of coordination number 6.
Ans. (b)
25. Assertion (A) : [Fe(CN)6]3– ion shows magnetic moment corresponding to two unpaired
electrons.
Reason (R) : Because it has d2sp3 type hybridisation.
Ans. (d)
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EXERCISE-4 MCQ, A/R, CASE-BASED QUESTIONS

INTRODUCTION
1. In K4[Fe(CN)6]
(a) (CN) are linked with primary valency (b) (CN) are linked with secondary valency
(c) K are linked with secondary valency (d) K are linked with non-ionic valency
2. Which of the following acts as a bidentate ligand in complex formation
(a) Acetate (b) Oxalate (c) Thiocyanate (d) EDTA
3. The co-ordination number of cobalt in the complex [Co(en)2Br2]Cl2 is
(a) 2 (b) 6 (c) 5 (d) 4
4. Which of the following ligands forms a chelate
(a) Acetate (b) Oxalate (c) Cyanide (d) Ammonia
®
5. According to Werner's theory
(a) Primary valency can be ionized
(b) Secondary valency can be ionized
(c) Primary and secondary valencies both cannot be ionized
(d) Only primary valency cannot be ionized
6. Which of the following is not true for ligand-metal complex
(a) Larger the ligand, the more stable is the metal-ligand bond
(b) Highly charged ligand forms strong bond
(c) Larger the permanent dipole moment of ligand, the more stable is the bond
(d) Greater the ionization potential of central metal, the stronger is the bond
7. Which is the example of hexadentate ligand
(a) 2, 2—dipyridyl (b) Dimethyl glyoxime
(c) Aminodiacetate ion (d) Ethylene diammine tetra acetate ion [EDTA]
8. The coordination number of a metal in coordination compounds is
(a) Same as primary valency (b) Sum of primary and secondary valencies
(c) Same as secondary valency (d) None of these
9. Ligand in a complex salt are
(a) Anions linked by coordinate bonds to a central metal atom or ion
(b) Cations linked by coordinate bonds to a central metal atom or ion
(c) Molecules linked by coordinate bonds to a central metal atom or ion
(d) Ions or molecules linked by coordinate bonds to a central metal atom or ion
10. The coordination number of a central metal atom in a complex is determined by
(a) The number of ligands around a metal ion bonded by sigma and pi-bonds both.
(b) The number around a metal ion bonded by pi-bonds
(c) The number of ligands around a metal ion bonded by sigma bonds
(d) The number of only anionic ligands bonded to the metal ion
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11. Potassium ferrocyanide is a
(a) Normal salt (b) Mixed salt (c) Double salt (d) Complex salt
12. That ion or molecule which forms a complex compound with transitional metal ion is called
(a) Recipient (b) Ligand (c) Coordinate ion (d) No special name
13. An example of a double salt is
(a) Bleaching powder (b) Hypo (c) K4[Fe(CN)6] (d) Potash alum
NOMENCLATURE OXIDATION
14. How many ions are produced in aqueous solution of [Co(H2O)6]Cl2
(a) 2 (b) 3 (c) 4 (d) 6
15. IUPAC name of [Pt(NH3)3(Br)(NO2)Cl]Cl is
(a) Triamminechlorobromonitroplatinum (IV) chloride
(b) Triamminebromonitrochloroplatinum (IV) chloride
®
(c) Triamminebromochloronitroplatinum (IV) chloride
(d) Triamminenitrochlorobromoplatinum (IV) chloride
16. The IUPAC name of [Ni(CO)4] is :
(a) Tetra carbonyl nickel (II) (b) Tetra carbonyl nickel (0)
(c) Tetra carbonyl nickelate (II) (d) Tetra carbonyl nickelate (0)
–
17. The oxidation number of Pt in [Pt(C2H4)Cl3] is
(a) + 1 (b) + 2 (c) + 3 (d) + 4
ISOMERISM AND MAGNETIC PROPERTIES
18. The number of unpaired electrons in the complex ion [CoF6]3– is (Atomic no. of Co = 27)
(a) Zero (b) 2 (c) 3 (d) 4
19. Which would exhibit co-ordination isomerism
(a) [Cr(NH3)6] [Co(CN)6] (b) [Co(en)2Cl2]
(c) [Cr(NH3)6]Cl3 (d) [Cr(en)2Cl2]+
20. [Co(NH3)5NO2]Cl2 and [Co(NH3)5(ONO)]Cl2 are related to each other as
(a) Geometrical isomers (b) Optical isomers
(c) Linkage isomers (d) Coordination isomers
21. [Co(NH3)5Br]SO4 and [Co(NH3)5SO4]Br are examples of which type of isomerism
(a) Linkage (b) Geometrical (c) Ionization (d) Optical
+3
22. [Ti(H2O)6] is paramagnetic in nature due to
(a) One unpaired (b) Two unpaired (c) Three unpaired (d) No unpaired
23. Coordination isomerism is caused by the interchange of ligands between the
(a) Cis and Trans structure (b) Complex cation and complex anion
(c) Inner sphere and outer sphere (d) Low oxidation and higher oxidation states
2– 2–
24. Amongst Ni(CO)4, [Ni(CN)4] and [NiCl4] [IIT 1991]
(a) Ni(CO)4 and [NiCl4] are diamagnetic and [Ni(CN)4]2– is paramagnetic
2–
(b) [NiCl4]2– and [Ni(CN)4]2– are diamagnetic and Ni(CO)4 is paramagnetic

(c) Ni(CO)4 and [Ni(CN)4]2– are diamagnetic and is paramagnetic
(d) Ni(CO)4 is diamagnetic and and [Ni(CN)4]2– are paramagnetic
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25. [Co(NH3)4Cl2]+ exhibits

(a) Geometrical isomerism (b) Optical isomerism
(c) Bonding isomerism (d) Ionisation isomerism
26. Which of the following compounds exhibits linkage isomerism
(a) [Co(en)3]Cl3 (b) [Co(NH3)6[Cr(CN)6]
(c) [Co(en)2 NO2Cl] Br (d) [Co(NH3)5Cl]Br2
27. The possible number of optical isomers in [Co(en)2Cl2] are
(a) 2 (b) 3 (c) 4 (d) 6
28. The number of unpaired electrons in Ni(CO)4 is
(a) Zero (b) One (c) Three (d) Five
HYBRIDISATION AND GEOMETRY
29. One mole of the complex compound Co(NH3)5Cl3 gives 3 moles of ions on dissolution in water.
®
One mole of the same complex reacts with two moles of AgNO3 solution to yield two moles of
AgCl(s). The structure of the complex is
(a) [Co(NH3)5Cl]Cl2 (b) [Co(NH3)3Cl3].2NH3
(c) [Co(NH3)4Cl2]Cl.NH3 (d) [Co(NH3)4Cl]Cl2.NH3
30. In the formation of K4[Fe(CN)6] the hybridisation involved is
(a) sp2 (b) d2sp3 (c) d3sp2 (d) d4p
31. Which complex has square planar structure
(a) Ni(CO)4 (b) [NiCl4]2– (c) [Ni(H2O)6]2+ (d) [Cu(NH3)4]2+
32. [CoF6]–3 is formed by ..... hybridization
(a) d2sp3 (b) d3sp2 (c) d2sp3 (d) sp3d2
ANSWER KEY
Q. No. 1 2 3 4 5 6 7 8 9 10
Ans. b b b d a b d c d c
Q. No. 11 12 13 14 15 16 17 18 19 20
Ans. d b d b c b b d a c
Q. No. 21 22 23 24 25 26 27 28 29 30
Ans. c a a c a c b a a b
Q. No. 31 32
Ans. d c
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ASSERTION AND REASON
Note : In the following questions a statement of assertion followed by a statement of reason is

given. Choose the correct answer out of the following choices.
1. Assertion (A) : In the coordination compound [Co(H2NCH2CH2NH2)3]2, ethane-l,2-diamine is a
neutral ligand.
®
Reason (R) : Oxidation number of Co in the complex ion is +3.
2. Assertion (A) : Isomers differ in one or more physical or chemical properties.
Reason (R) : These have different arrangement of atoms.
3. Assertion (A) : Tetrahedral complexes do not show geometrical isomerism.
Reason (R) : The relative positions of the unidentate ligands attached to the central metal atom
are the same with respect to each other.
4. Assertion (A) : Oxidation number of Cr in [Cr(NH3)3(H2O)3]Cl3 is same as the charge of the
complex ion, +3.
Reason (R) : All the ligands are neutral molecules in this compound.
5. Assertion (A) : The stability of [Ni(en)3] Cl2 is lower than that of [Ni(NH3)6] Cl2.
Reason (R) : The geometry of Ni is trigonal bipyramidal in[Ni(en)3] Cl2.
6. Assertion (A) : The ligands of nitro and nitrito are called ambidentate ligands.
Reason (R) : These ligands give linkage isomers.
7. Assertion (A) : [Pt Cl2 (NH3)2] is square planner
Reason (R) : Cl- is a weak field ligand

8. Assertion (A) : [Cr(H2O)6]Cl2 and [Fe(H2O)6]Cl2 are reducing in nature.
Reason (R) : Unpaired electrons are present in their d-orbitals.

9. Assertion (A) : [Ni(CO)4] is SP3 hybridized
Reason (R) : It is diamagnetic in nature.

10. Assertion (A) : Ionisation isomerism shown by compounds having same composition.
Reason (R) : Compounds having same ions in the solutions.
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11. Assertion (A) : Coordination compounds show linkage isomerism.

Reason (R) : They have ambidentate ligands.
12. Assertion (A) : [Co(NH3)5SO4]Br and [Co(NH3)5Br]SO4 show ionisation isomerism.
Reason (R) : Because they have Co metal.
13. Assertion (A) : Heteroleptic complexes show geometrical isomerism.
Reason (R) : Complexes with coordination number 6 and 8 are heteroleptic.
®
ANSWER KEY
Q. No. 1 2 3 4 5 6 7 8 9 10
Ans. b a a a c a b b b c
Q. No. 11 12 13
Ans. a c c
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CASE BASED QUESTIONS

Case-I
Crystal field theory was proposed by H. Bethe and van Vleck in 1930. L.Orgel in 1952, gave a
much more satisfactory explanation for the bonding and the properties of complexes. The crystal
field theory (CFT) is an electrostatic model which considers the metal-ligand bond to be ionic
arising purely from electrostatic interactions between the metal ion and the ligand. In an
octahedral coordination entity with six ligands surrounding the metal atom/ion, there will be
repulsion between the electrons in metal d-orbitals and the electrons (or negative charges) of the
ligands. Such a repulsion is more when the metal d-orbital is directed towards the ligand than
when it is away from the ligand.
The degeneracy of the d-orbitals has been removed due to ligand-metal electron repulsions in the
octahedral complex to yield three orbitals of lower energy, t2g set and two orbitals of higher
energy, eg set.
®
The splitting of d-orbitals in an octahedral crystal field can be seen in following diagram.
Energy
Z
eg
Y
3/5 0
X
Bary centre
0
Metal Average 2/5 0
d-orbital energy
of the d-
orbitals in dxy dxz dyz t2g
spherical Splitting of d-orbitals
crystal field in octahedral
Free metal ion
crystal field
(a) What is crystal field splitting energy ?

Ans. The difference of energy between two sets of d-orbitals after splitting is called crystal field
splitting energy or crystal field stabilisation energy (CFSE).
OR
What is the basis of formation of spectro-chemical series ?
Ans. Spectrochemical series : The arrangements of ligands in the order of their increasing field
strength, i.e., increasing crystal field splitting energy (CFSE) value is called
spectrochemical series.
Crystal field splitting energy is the basis of formation of the spectrochemical series.
(b) Predict the number of unpaired electrons and magnetic nature in the square planar
[Pt(CN)4]2– ion.
Ans. 78Pt is present in group 10 of the periodic table.
Its outer configuration is 5d96s1.

5d 6s 6p
Pt2+(5d86s0) =
= ×× ×× ×× ××
–
CN CN– CN– CN–
dsp2-hybridisation
=
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CN– is a strong field ligand. It causes pairing of 5d unpaired electrons which mnakes one d-
orbital empty for dsp2-hybridisation and form square planar complex. As, there are no
unpaired electrons in [Pt(CN)4]2– ion.
=0
(c) Answer the following :
(i) Which of the two K4[Fe(CN)6] or K3[Fe(CN)6] is more stable and why?
(ii) What are the various factors affecting crystal field splitting ?
Ans. (i) In K4[Fe(CN)6], oxidation state of Fe is +2.
In K3[Fe(CN)6], oxidation state of Fe is +3.
Therefore, electronic configuration of
Fe2+ = d6 = t 62g
®
Fe3+ = d5 = t 52g
C.F.S.E. of K4[Fe(CN)6] = –0.4 × 6 0 = –2.4 0
C.F.S.E. of K3[Fe(CN)6] = –0.4 × 5 0 = –2.0 0
More is the C.F.S.E. more is the stability of the complex. Therefore, K4[Fe(CN)6] is more
stable than K3[Fe(CN)6].
(ii) The crystal field splitting, 0 depends upon the field produced by the ligand and charge
on the metal ion.
Some ligands are able to produce strong fields in thatcase, the splitting will be large,
whereas others produces weak field and consequently results in small splitting of
d-orbitals.
Case II
Isomerism is a phenomenon in which compounds have the same molecular formula but different
physical and chemical properties on account of different structures. The two major types of
isomerism are structural and stereoisomerism. The structural isomerism is further divided into
four types:
Linkage, coordination, ionisation and solvate isomerism.
While, the stereoisomerism is divided into two types :
Geometrical and Optical isomerism.
(a) What is meant by the term ionisation isomerism ?

Ans. Ionisation isomerism arises when compounds give different ions in the solution, althught
they have same composition.
(b) What type of coordination compounds show linkage isomerism ?
Ans. Linkage isomerism is shown by the coordination compounds containing ambidendate
ligands.
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(c) [Co(NH3)5(NO2)] (NO3)2 shows ionisation isomers as follows :
[Co(NH3)5(NO2)] (NO3)2 and [Co(NH3)5(NO3)] (NO2) (NO3).
Suggest an alternative isomerism exhibited by the given compound and also give the
number of ions produced from the complex.
Ans. [Co(NH3)5(NO2)] (NO3)2 shows linkage isomers as follows :
[Co(NH3)5(NO2)] (NO3)2 and [Co(NH3)5(NO3)] (NO2) (NO3)
The complex will dissociate in aqueous soluiton to produce three ions.
[Co(NH3)5(NO2)] (NO3)2 [Co(NH3)5(NO2]2+ + 2NO3
OR
Write all the isomers of :
®
(i) [Co(NH3)6] [Cr(C2O4)3]
(ii) [Co(NH3)5SO4] Br
Ans. (i) The given compound exhibits coordination isomerism. The two isomers are :
(a) [Co(NH3)6] [Cr(C2O4)3] (b) [Co(C2O4)3] [Cr(NH3)6]
(ii) The given compound exhibits ionisation isomerism . The two isomers are :
(a) [Co(NH3)5SO4] Br (b) [Co(NH3)5Br] SO4
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PREVIOUS YEARS QUESTIONS

SECTION-A (ONE MARK QUESTIONS)
1. What is the secondary valency of Cobalt in [Co(en2)Cl2]+ ? [1] (CBSE _2023)
(a) 6 (b) 4 (c) 2 (d) 8
Ans. (a)
2. Which of the following ligands is an ambidentate ligand ? [1] (CBSE _2023)
(a) CO (b) NO2 (c) NH3 (d) H2O
Ans. (b)
3. The formula of the complex Iron (III) hexacyanidoferrate (II) is : [1] (CBSE _2023)
(a) Fe2 [Fe(CN)6]3 (b) Fe4 [Fe(CN)6]3
(c) Fe [Fe(CN)6] (d) Fe 3 [Fe(CN) 6 ]2
®
Ans. (b)
4. The oxidation state of Fe in [Fe(CO)5] is [1] (CBSE _2023)
(a) 2 (b) 0 (c) +3 (d) +5
Ans. (b)
5. The formula of the complex dichloridobis (ethane –1, 2-diamine) platinum (IV) nitrate is
[1] (CBSE _2023)
(a) [Pt Cl2(en)2 (NO3)2] (b) [Pt Cl2(en)2] (NO3)2
(c) [Pt Cl2(en)2(NO3)] NO3 (d) [Pt (en)2(NO3)2] Cl2
Ans. (b)
6. Draw the geometrical isomers of [CoCl2(en)2]+. [1] (Compartment _CBSE 2021)
Cl Cl
Cl
en Co en Co en
Ans.
en Cl
Cis Trans Mirror
7. Assertion (A) : Linkage isomerism arises in coordination compounds becauses of ambidentate ligand.
Reason (R) : Ambidentate ligand like NO2 has two different donor atoms i.e., N and O.
[1] (CBSE 2020)
Ans. (i) Both Assertion (A) and Reason (R) are correct statement and Reason (R) is the correct
explanation of the Assertion(A)
8. Give the formulae of the following compounds : [1] (CBSE 2020)
(i) Potassium tetra hydroxydozincate [II]
(ii) Hexaammine platinium [IV] Chloride
Ans. (i) K2[Zn(OH)4] (ii) [Pt(NH3)6]Cl4
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ALLEN
9. Write the coordination number and oxidation state of Platinum in the complex [Pt(en)2Cl2].
[1] (CBSE 2018)
Ans. Given complex [Pt (en)2 Cl2]
Coordination no. = denticity × no. of ligands = 2 × 2 + 1× 2 = 6
Charge on ligand + oxidation state = charge on complex of metal ion = –2 + x = 0
Oxidation tate of Pt = x
x + 2(0) + 2(–1) = 0
x  2
SECTION-B (TWO MARKS QUESTIONS)

10. (a) Write the IUPAC names of the following : [2] (CBSE 2023)
2+
(i) [Co(NH3)5(ONO)]
®
(ii) K2[NiCl4]
OR
(b) (i) What is chelate complex? Give on example.
(ii) What are heteroleptic complexes ? Give one example.
Ans. (a) (i) Pentaamminenitrito – O-cobalt (III)
(ii) Potassium tetrachloridonickelate (II)
OR
(b) (i) When a di- or polydentate ligand uses its two or more donor atoms to bind a single
metal ion, it is said to be a chelate ligand. Such complexes, called chelate complexes
eg. EDTA4–.
(ii) Complex in which a metal is bound to more then are kind of donor group
eg.[Co(NH3)5(ONO)]2+
11. Write IUPAC name of the complex [Co(en)2(NO2)Cl]+. What type of structural isomerism is
shown by this complex ? [2] (CBSE 2019)
OR
Using IUPAC norms, write the formulae for the following complexes :
(a) Hexaaquachromium (III) chloride (b) Sodium trioxalatoferrate (III)
Ans. Chloridobis(ethane-1,2-diamine)nitrito-N-cobalt(III)ion
Linkage isomerism
OR
(i) [Cr(H2O)6]Cl3 (ii) Na3[Fe(OX)3]
12. (a) Although both [NiCl4]2– and [Ni(CO)4] have sp3 hybridisation yet [NiCl4]2– is paramagnetic
and [Ni(CO)4] is diamagnetic. Give reason. (Atomic no. of Ni = 28)
(b) Write the electronic configuration of d5 on the basis of crystal field theory when
(i) 0 < P and (ii) 0 > P [2] (CBSE 2019)
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Ans. (a) In [NiCl4]2, Cl is a weak field ligand due to which there are two unpaired electrons in 3d
orbital whereas in [Ni(CN)4]2, CN is a strong field ligand due to which pairing leads to no
unpaired electron in 3d-orbital/Or structural representation.
(b) (i) t2g3eg2 (ii) t2g5eg0
13. Defind the following terms with a suitable example of each :
(a) Chelate complex (b) Ambidentate ligand [2] (CBSE 2019)
OR
Using IUPAC norms, write the formulae for the following complexes : [2]
(a) Tetraamminediaquacobalt(III) chloride
(b) Dibromidobis(ethane-1, 2-diamine)platinum(IV) nitrate
Ans. (a) When a di- or polydentate ligand uses its two or more donor atoms to bind a single metal
ion, it is said to be a chelate ligand. The number of such ligating groups is called the
®
denticity of the ligand. Such complexes, called chelate complexes
(b) Ligand which can ligate through two different atoms is called ambidentate ligand.
OR
(a) [Co(NH3)4(H2O)2] Cl3
(b) [Pt Br2(en)2] [NO3)2]
14. Using valence bond theory, write the hybridisation and magnetic character of the complex
[Fe(CN)6]4–. (Atomic no. of Fe = 26) [2] (CBSE 2019)
Ans. d2 sp3; Diamagnetic nature
15. Defind the following terms with a suitable example of each : [2] (CBSE 2019)
(a) Polydentate ligand (b) Homoleptic complex
OR
Using IUPAC norms, write the formulae for the following complexes : [2]
(a) Potassium tri(oxalato)chromate(III)
(b) Hexaaquamanganese(II) sulphate
Ans. (a) Polydentate ligands range in the number of atoms used to bond to a central metal atom or ion.
e.g. EDTA
(b) Homoleptic complex are those which has all identical ligand. e.g. metal compound
OR
(a) K3 [Cr(OX)3]
(b) [Mn(H2O)6]SO4
16. Using IUPAC norms write the formulae for the following :
(a) Tris (ethane-1,2-diamine)chromium(III)chloride
(b) Potassium tetrahydroxozincate(II) [2] (CBSE 2018)
Ans. (a) [Cr(en)3]Cl3
(b) K2[Zn(OH)4]
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17. (a) For the complex [Fe(CN)6]4–, write the hybridization, magnetic character and spin type of
thecomplex. (At. number : Fe = 26)
(b) Draw one of the geometrical isomers of the complex [Co(en)2Cl2]+ which is optically
active. [2] (CBSE 2018)
Ans. (a) d2sp3,
Diamagnetic, low spin
Cl +
Cl
(b) en Co
en
18. When a coordination compound NiCl2.6H2O is mixed with AgNO3, 2 moles of AgCl are
precipitated per mole of the compound. Write [2] (CBSE 2018)
®
(i) Structural formula of the complex
(ii) IUPAC name of the complex
Ans. (i) [Ni(H2O)6] Cl2
(ii) Hexaaquanickel(II) chloride
SECTION-C (THREE MARKS QUESTIONS)
19. (a) Draw the geometrical isomers of [Co(en)2Cl2]2+. Which geometrical isomer of
[Co(en)2Cl2]2+ is not optically active and why ?
(b) Write the hybridisation and magnetic behaviour of [CoF6]3–
[Given: Atomic number of Co = 27] [3] (CBSE 2023)
+
Ans. (a) [CoCl2(en)2]
Cl Cl
en Co Co en
en en
Cl Cl
Mirror
+
Trans [CoCl2(en)2] isomer-optically inactive
(Superimposable mirror images)
Cl Cl
Cl Cl
en Co Co en
en en
Mirror
+
Cis [CoCl2(en)2] isomer-optically active
(non-superimposable mirror images)
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(b) [CoF6]3–
Cobalt exists in the +3 oxidation state.
3+
Orbitals of Co ion
3d 4s 4p 4d
3 2
sp d hybridised
3+
orbitals of Co
3 2
3d sp d hybrid 4d
3–
[CoF 6]
(outer orbital or
high spin complex)
3d six pairs of electrons 4d
from six F– ions
20. (a) Using valence bond theory, predict the hybridization and magnetic character of following :
[CoF6]3– [Atomic number of Co = 27]
(b) Write IUPAC name of the following complex : [CoBr2(en)2]+
®
(c) How many ions are produced from the complex [Co(NH3)6]Cl2 in solution ?
[1× 3 = 3](CBSE-Term-II_ 2022)
Ans. (a) [CoF6]3– Hybridization = sp3d2
Magnet character = Paramagnetic
(b) dibromidobis – ethane-1,2-diamine.cobalt(I)
(c) [Co(NH3)6]Cl2 [Co(NH3)6]3+ + 2Cl–
(aq. sol.) 3 ions produced
21. (i) Write the IUPAC name of the complex [Cr(NH3)4 Cl2] Cl.
(ii) What type of isomerism is exhibited by the complex [Co(en)3]3+ (en = ethane-1,2-diamine)
(iii) Why is [NiCl4]2– paramagnetic but [Ni(CO)4] is diamagnetic ?
(At. nos. : Cr = 24, Co = 27, Ni = 28) [3] (CBSE 2020)
Ans. (i) Tetraamminedichloridochromium(III) chloride
3+ 3+
en
en
(ii) en Co Co en
en en
dextro mirror laevo
Optical Isomer
(iii) In Ni(CO)4, Ni is in zero oxidation state whereas in NiCl42–, it is in +2 oxidation state. In

the presence of CO ligand, the unpaired d electrons of Ni pair up but Cl– being a weak
ligand is unable to pair up the unpaired electrons.
22. What is meant by crystal field splitting energy? On the basis of crystal field theory, write the
electronic configuration of d4 in terms of t2g and eg in an octahedral field when
(i) 0 >P (ii) 0 <P [3] (CBSE 2020)
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Ans. The difference of energy two sets of d-orbitals (which are no longer degenerate under different
kinds of electric fields).
Is called crystal field stabilization energy or (CFSE) represented by symbol 0 .
d4 when 0 >P t42geg°.
d4 when 0 <P t32geg1.
23. For the complex [NiCl4]2–, write
(i) the IUPAC name
(ii) the hybridization type.
(iii) the shape of the complex
(Atomic no. of Ni = 28) [3] (CBSE 2020)
Ans. [NiCl4] 2–
®
(i) Tetrachlorido nickelate (II) ion
(ii) sp3
(iii) tetrahedral
24. Name the following coordination entities and draw the structures of their stereoisomers :
(i) [Co(en)2Cl2]+ (en = ethylenediamine)
(ii) [Cr(C2O4)3]3–
(iii) [Co(NH3)3Cl3]
(Atomic numbers Cr = 24, Co = 27) [3] (CBSE 2019)
Ans. (i) Dichlorido bis ethylenediamine cobalt (III) ion
Cl Cl
Cl
en Co en Co
en
en Cl
Cis Trans
(ii) Trioxalato chromate (III) ion
ox ox
ox Co Co ox
ox ox
3–
[Cr(OX)3] Mirror [Cr(OX)3]3–
(dextro) (Laevo)
(iii) Triamine trichlorido cobalt (III)
NH3 NH3
Cl NH3 NH3 Cl
Co Co
Cl NH3 Cl Cl
Cl NH3
Fac mer
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E 319
25. Explain the following terms giving a suitable example in each case :
(i) Ambidentate ligand
(ii) Denticity of a ligand
(iii) Crystal field splitting in an octahedral field [3] (CBSE 2019)
Ans. (i) Ambidentate ligand : Ligand which can link through two different atoms is called
ambident ligand. Example - SCN-, CNO–, CN-, NO 2 can link through ‘N’ as well as O
while SCN– can link through ‘S’ as well ‘N’ atom.
(ii) Denticity of a ligand : Total number of lone pair donated by a ligand when it is bonded
with metal is called denticity or number of doner sites on a ligand is called denticity.
CN- has 1, COO-
has 2,
COO-
H2N – CH2 – CH2 – NH – CH2 – CH2 – NH2 has 3.
(iii) Crystal field spliting in an octahedral field : In a octahedral complex, the co-ordination
®
number is 6. The metal ion is at the centre and the ligands occupy the six corners of the
octahedron as shown in figure.
We know that two orbitals, d x 2 y 2 and d z 2 are oriented along the axis while the remaining
three orbitals, viz., dxy, dyz and dzx are oriented in between the axis.
The two orbtials d x 2 y2
and d z 2 are designated as eg orbitals while the three orbitals d xy, dyz
and dzx are designated as t2g orbitals. As the six ligands approach the central ion along the
axis, eg orbitals, is repelled more by the ligand than the t2g orbitals.
Z
In other words, the energy of the d z 2 and d x 2 y2

orbitals increases much more than the
energy of the dxy, dyz and dzx orbitals.
Thus, in octahedral complexes, the five d-orbitals split up into two sets : one set
consisting of two orbitals ( d x2 – y2 and ) of higher energy (eg orbitals) and the other set
consisting of three orbitals (dxy, dyz and dzx ) of lower energy (t2g orbitals).
eg
.6
–.4
t2g
The state I represents degeneracy of al the five d-orbitals in the isolated central ion. The
state II represents hypothetical degeneracy of all the orbitals at a higher energy level if the
negative charge of all the ligands is assumed to be uniformly affecting the electrons in the
d-orbitals of the metal ion. The state III represents crystal field splitting discussed above
TG: @Chalnaayaaar
320 E
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CBSE
26. Explain the following cases giving appropriate reasons:
(i) Nickel does not form low spin octahedral complexes.
(ii) The -complexes are known for the transition metals only.
(iii) Co2+ is easily oxidised to Co+3 in the presence of a strong ligand. [3] (CBSE 2019)
Ans. (i) Since nickel in zero oxidation state contain no unpaired electron.
(ii) The transition metal/ions have electrons in d- orbitals which can be shared to -acid
ligands through synergic bonding.
For example : CH2 = CH2 and C6 H6 etc.
(iii) Co3+ can from very stable low spin octahedral complex.
27. Compare the following complexes with respect to structural shapes of units, magnetic behaviour
and hybrid orbitals involved in units :
®
[Co(NH3)6]3+, [Cr(NH3)6]3+, Ni(CO)4
(At. Nos. : Co = 27, Cr= 24, Ni = 28) [3] (CBSE 2019)
Ans. S. No. Complexes Magnetic behaviour Hybridisation Shape

3+
1 [Co(NH3)6] Diamagnetic d2sp3 Octahedral
3+ 2 3
2 [Cr(NH3)6] Paramagnetic d sp Octahedral
3 [Ni(CO)4] Diamagnetic sp3 Tetrahedral
28. Giving a suitable example for each, explain the following :

(i) Crystal field splitting
(ii) Linkage isomerism
(iii) Ambidentate ligand [3] (CBSE 2019)
Ans. (i) Crystal field splitting : In a free transition metal ion, all the five orbitals are degenerate,
but when it is involved in a complex formation, the degeneracy split. This is called crystal
field splitting.
(ii) Linkage isomerism : Linkage isomerism arises in a coordination compound containing
ambidentate ligand. A simple example is provided by complexes containing the thiocyanate
ligand, NCS–.
(iii) Ambidentate ligand : Unidentate ligands containing more than one coordinating atoms are
called ambidentate ligands. For example,
NO–2, CN–, SCN– are all ambidentate ligands.

29. (a) What is the basis of formation of the spectro-chemical series ?
(b) Draw the structures of geometrical isomer of the following coordination complexes :
[Co(NH3)3Cl3] and [CoCl2(en)2]+
(en = ethylenediamine and atomic number of Co is 27) [3] (CBSE 2019)
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E 321
Ans. (a) Spectro-chemical series : The arrangement of ligands are in their increasing
field strength i.e. increasing crystal field splitting energy (CFSE) value, is called spectro-
chemical series. Crystal field splitting energy is the basis of formation of the spectro
chemical series.
It is an experimentally determined series based on the absorption of light by complexes
with different ligands.
I– <Br–< SCN– < Cl– < S2–< F–< OH–< C2O42–< H2O < NCS–< edta4–< NH3 < en < CN–<CO
(b) (i) The cis and trans isomers of [Co(NH3)3Cl3] may be represented as
Cl NH3 NH3 NH3
NH3 Cl
Co Co
Cl NH3 Cl Cl
®
Cl NH3
cis-isomer trans-isomer
+
(ii) [CoCl2 (en)2] ion exists in two geometrical isomers as shown below.
Cl Cl
Cl
en en
Co Co
en
Cl en
trans-isomer cis-isomer
30. (a) Write the formula of the following coordination compound :
Iron(III) hexacyanoferrate(II)
(b) What type of isomerism is exhibited by the complex [Co(NH3)5Cl]SO4 ?
(c) Write the hybridisation and number of unpaired electrons in the complex [CoF6]3–.
(Atomic No. of Co = 27). [3] (CBSE 2018)
Ans. (a) Fe4[Fe(CN)6]3
(b) [CO(NH3)5Cl]SO4 (Ionisation isomers)
(c) [COF6]–3
(i) Hybridisation Sp3d2
(ii) Unpaired e– 4 unpaired electrons.
31. (a) What type of isomerism is shown by the complex [Co(NH3)5(SCN)]2+ ?
(b) Why is [NiCl4]2– paramagnetic while [Ni(CN)4]2– is diamagnetic ?
(Atomic number of Ni = 28)

(c) Why are low spin tetrahedral complexes rarely observed [3](CBSE 2018)
Ans. (a) Linkage isomerism
(b) In [NiCl4]2–, due to the presence of Cl–, a weak field ligand no pairing occurs whereas in
[Ni(CN)4]2–, CN–is a strong field ligand and pairing takes place.
(c) Because of very low CFSE which is not able to pair up the electrons.
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322 E
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CBSE
SECTION-D (FOUR MARKS QUESTIONS)

32. In an octahedral coordination entity with six ligands surrounding the metal atom/ion, there will
be repulsion between the electrons in metal d orbitals and the electrons (or negative charges) of
the ligands. Such a repulsion is more when the metal d orbital is directed towards the ligand than
when it is away from the ligand. Thus, the dx2-y2 and dz2 orbitals.
Which point towards the axes along the direction of the ligand will experience more repulsion
and will be raised in energy; and the dxy, dyz and dxz orbitals which are directed between the
axes will be lowered in energy relative to the average energy in the spherical crystal field. Thus,
the degeneracy of the d orbitals has been removed due to ligand electron-metal electron
repulsions in the octahedral complex to yield three orbitals of lower energy, t2g set and two
orbitals of higher energy, eg set. ?
®
Answer the following questions :
(a) Write the relation between t and O.
4
Ans. t = O
9
(b) Why is CO a stronger ligand than Cl– ?
Ans. It is because CO can form (sigma) as well as -bond.
(c) What is spectrochemical series? Explain the difference between a weak field and a strong
field ligand.
Ans. A spectrochemical series is the arrangement of common ligands in the increasing order of
their crystal - field splitting energy (CFSE) values. The ligands present on the R.H.S of the
series are strong field ligands while that on the L.H.S are weak field ligands. Also, strong
field ligands cause higher splitting in the d orbitals that weak field ligands.
I– < Br– < S2– < SCN– <Cl– <N3– < OH– < C2O42– < ~H2O < NCS– < edta4– < NH3 < en– < CN– < CO
OR
What is meant by crystal field splitting energy? On the basis of crystal field theory, write
the electronic configuration of d4 in terms of t2g and eg in an octahedral field when
(i) 0 >P (ii) 0 <P

Ans. The difference of energy two sets of d-orbitals (which are no longer degenerate under
different kinds of electric fields).
Is called crystal field stabilization energy or (CFSE) represented by symbol 0.
d4 when 0 >P t42g eg°.

d4 when 0 <P t32g eg1.
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E 323
SECTION-E (FIVE MARKS QUESTIONS)
33. (i) What type of isomerism is shown by [Co(NH3)5ONO]Cl2 ?

(ii) On the basis of crystal field theory, write the electronic configuration for d4 ion if 0
< P.
(iii) Write the hybridization and shape of [Fe(CN)6]3–.
(Atomic number of Fe = 26)
(iv) Write down the IUPAC name of the following complex :
[Pt(NH3)(H2O)Cl2]
(v) Write the formula for the following complex :
tris(ethan-1, 2-diamine)chromium(III) chloride [5] (CBSE 2018)
®
Ans. (i) Linkage isomerism
(ii) t2g3 eg1 / Diagrammatic representation
(iii) d2sp3, Octahedral

(iv) Ammineaquadichloridoplatinum(II)
(v) [Cr(en)3]Cl3
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324 E
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CBSE
PRACTICE TEST
SECTION-A
1. The name of complex ion, [Fe(CN)6]3– is :- [1]
(a) Tricyanoferrate (III) ion (b) Hexacyanidoferrate (III) ion
(c) Hexacyanoiron (III) ion (d) Hexacyanitoferrate (III) ion
2. The hybridization involved in complex [Ni(CN)4]2– is (At.No. Ni = 28) [1]
(a) d2sp2 (b) d2sp3 (c) dsp2 (d) sp3
3. The sum of coordination number and oxidation number of the metal M in the complex
[M(en)2(C2O4)]Cl (where en is ethylenediamine) is :- [1]
(a) 7 (b) 8 (c) 9 (d) 6
4. Which one of the following electrolytes has the same value of van't Hoff's factor (i) as that of the
®
Al2(SO4)3 (if all are 100% ionised) ? [1]
(a) K3[Fe(CN)6] (b) Al(SO4)3
(c) K4[Fe(CN)6] (d) K2SO4
5. Crystal field stabilization energy for high spin d4 octahedral complex is :- [1]
(a) –0.6 0 (b) –1.8 0 (c) –1.6 0 + P (d) –1.2 0
Note : In the following questions a statement of assertion followed by a statement of reason is
given. Choose the correct answer out of the following choices.
6. Assertion (A) : [Ni(CN)4]2– is square planar and diamagnetic.
Reason (R) : It has no unpaired electrons due to presence of strong field ligand. [1]
7. Assertion (A) : The total number of isomers shown by [Co(en)2Cl2 l+ complex ion is three.
Reason (R) : [Co(en)2Cl2]+ complex ion has an octahedral geometry. [1]
SECTION-B
8. Why is [NiCl4]2– paramagnetic while [Ni(CN)4]2– is diamagnetic ?
(Atomic number of Ni = 28) [2]
9. Write the corrdination number and oxidation state of Platinum in the complex [Pt(en)2Cl2]. [2]
10. Write the hybridisation and number of unpaired electrons in the complex [CoF6]3–.
(Atomic No. of Co = 27). [2]
11. When a coordination compound NiCl2.6H2O is mixed with AgNO3, 2 moles of AgCl are
precipitated per mole of the compound. Write [2]
(i) Structural formula of the complex
(ii) IUPAC name of the complex
TG: @Chalnaayaaar
E 325
SECTION-C
12. Using IUPAC norms write the formulae for the following : [3]
(a) Tris (ethane-1,2-diamine)chromium(III)chloride
(b) Potassium tetrahydroxozincate(II)
(c) Hexaammine platinium [IV] Chloride
13. For the complex [Fe(CN)6]4–, write the hybridization, magnetic character and spin type of the
complex. (At. number : Fe = 26) [3]
SECTION-D
14. The Lewis approach to chemical bonding failed to shed light on the formation of chemical bonds.
Also, valence shell electron pair repulsion theory of (VSEPR theory) has limited applications
(and also failed in predicting the geometry corresponding to complex molecules). In order to
®
address these issues, the valence bond theory was put forth by the German physicists Walter
Heinrich Heitler and Fritz Wolfgang London. The Schrodinger wave equation was also used to
explain the formation of a covalent bond between two hydrogen atoms. This theory focuses on
the concepts of electronic configuration, atomic orbitals (and their overlapping) and the
hydridization of these atomic orbitals. Chemical bonds are formed from the overlapping of
atomic orbital wherein the electrons are localized in the corresponding bond region. the valence
bond theory also goes on to explain the electronic structure of the molecules formed by this
overlapping of atomic orbitals. It also emphasizes that the nucleus of one atom in a molecule is
attracted to the electrons of the other atoms. [1+1+2=4]
Answer the following questions :
(a) What type of hybrid orbital is associated with Ni atom in [Ni(CN)4]2– ?
OR
What is the oxidation coordination number of central metal ion in [Fe(C2O4)3]3– ?
(b) Using valence bond theory predict the shape of [Ni(CO)4].[Ni = 28]
(c) For the complex, [Fe(en)2Cl2]Cl (en = ethylenediamine), identify and write :
(i) oxidation number of iron
(ii) number of hybrid orbitals and the shape of the complex.
SECTION-E
15. (a) What is meant by crystal field splitting energy? On the basis of crystal field theory, write
the electronic configuration of d4 in terms of t2g and eg in an octahedral field when [5]
(i) 0
>P
(ii) 0
<P
(b) (i) Write the IUPAC name of the complex [Cr(NH3)4 Cl2] Cl.
(ii) Write IUPAC name of the complex [Co(en)2(NO2)Cl]+.
(iii) Why is [NiCl4]2– paramagnetic but [Ni(CO)4] is diamagnetic ?
(At. nos. : Cr = 24, Co = 27, Ni = 28)
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326 E
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CBSE
PRACTICE TEST SOLUTIONS

SECTION-A
1. (b)
2. (c)
3. (c)
4. (b)
5. (a)
6. (a)
7. (b)
SECTION-B
8. In [NiCl4]2–, due to the presence of Cl¯, a weak field ligand no pairing occurs whereas in
®
[Ni(CN)4]2, CN¯ is a strong field ligand and pairing takes place.
9. Given complex [Pt (en)2 Cl2]
Coordination no. = denticity × no. of ligands
=2×2+2×1=6
Charge on ligand + oxidation state = charge on complex of metal ion
–2+x=0
x = +2
10. [COF6]–3
(i) Hybridisation Sp3d2
(ii) Unpaired e¯ 4 unpaired electrons.
11. (i) [Ni(H2O)6] Cl2
(ii) Hexaaquanickel(II) chloride
SECTION-C
12. (i) [Cr(en)3]Cl3
(ii) K2[Zn(OH)4]
(iii) [Pt(NH3)6]Cl4
13. d2sp3,
Diamagnetic,
low spin
SECTION-D
2
14. (a) dsp
OR
+3
TG: @Chalnaayaaar
E 327
(b) Oxidation state of Ni in Ni(CO)4 is zero.

3d 4s 4s
Ni (28) E.C. =
Hybridisation =
sp3 hybridisation
Ni(CO)4 =
Four pairs of electrons
from four CO molecules
Shape - Tetrahedral
®
Hybridisation - sp3
(c) (i) Let the oxidation number of iron (Fe) be x in [Fe(en)2Cl2]Cl.
x + 0 + 2 (–1) = +1 ; x = +3
3d5 4s0
(ii) Fe3+ = [Ar] 3d5 4s0 =
Fe3+ (in presence of ligand)

[Fe(en)2Cl2]–
×××× ×× ××××××
d2sp3-hybridisation
d2sp3 - hybridisation (six hybrid orbitals)
Shape - Octahedral
SECTION-E
15. (a) The difference of energy two sets of d-orbitals (which are no longer degenerate under
different kinds of electric fields).
Is called crystal field stabilization energy or (CFSE) represented by symbol 0.
d4 when 0 >P t42g eg°.

d4 when 0 <P t32g eg1.
(b) (i) Tetraamminedichloridochromium(III) chloride.

(ii) Chloridobis(ethane-1,2-diamine)nitrito-N-cobalt(III)ion.
(iii) In Ni(CO)4, Ni is in zero oxidation state whereas in NiCl42–, it is in +2 oxidation
state. In the presence of CO ligand, the unpaired d electrons of Ni pair up but Cl¯
being a weak ligand is unable to pair up the unpaired electrons.
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328 E

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[Cu(NH3)4]SO4 Ionization sphere/Counter ion

Ligand Coordination number

(e) Oxidation State

(h) Naming of ligands

Cationic monodentate ligands :

Anionic monodentate ligands :

CH2 CH NH CH2 CH CH2–CH2–NH–CH2–CH2–NH–CH2–CH2

H2 N NH2 H2N NH2

OOC CH2 CH2 COO

– +  bond / back bond

[Schematic of orbital overlaps in metal carbonyls]

Conclusion of synergic bonding :

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

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

This is a diamagnetic complex.

This is a paramagnetic complex.

e– configuration of 28Ni = [Ar] 3d8 4s2

It is inner orbital complex

(C) Crystal field theory

The two orbitals d x 2

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

Calculation of crystal field stablizing energy (CFSE)

n eg = number of electron in eg orbitals

Factors affecting splitting energy ( )

(v) number of ligands

APPLICATION OF CRYSTAL FIELD THEORY

difference in their structure are called as Isomers.

(A) Structural isomerism (B) Stereo isomerism

Ionization Hydrate Coordination Linkage Geometrical Optical

Ex. (i) [Zn(NH3 )4 ZnCl 4 ]

(B) Stereo Isomerism

(i) Geometrical Isomerism

Ex. [Pt (NH3)2Cl2]

Geometrical isomers with Coordination number = 6 (Octahedral complex)

(ii) [Ma4bc] has 2 geometrical isomers

(iii) Facial and Meridional isomerism (Ma3b3 )

(B) Optical Isomers

(ii) [M(AA)2ab]n+ [Co(en)2NH3Cl]2+

APPLICATION OF COORDINATION CHEMISTRY

EXERCISE-1 INTEXT QUESTIONS

(iii) Cr(en)3 Cl3 (iv) Pt(NH)3 BrCl(NO2 )

(v) K 2 PdCl4 (vi) Pt(NH 3 ) 2Cl(NH 2CH 3 ) Cl

Trans-isomer is optically inactive. On the other hand, cis-isomer is optically active.

(ii) Two-optical isomers for CO(en)3 Cl3 exist.

It can also show linkage isomerism

(iv) Geometrical (cis-, trans-) isomers of Pt(NH3 ) (H 2O)Cl 2 can exist.

[CO(NH3)5Cl]SO4 + Ba2+ BaSO4

Since there are 2 unpaired electrons in this case, it is paramagnetic in nature.

unpaired electrons are present in this case, [Ni(CO)4] is diamagnetic.

Therefore, = n(n 2) = 1(1 2) = 3 = 1.732 BM

Therefore, n(n 2) = 5(5 2) = 35 = 6 BM

Ans. [Co(NH3)6]3+ [Ni(NH3)6]2+

EXERCISE-2 NCERT EXERCISE

CuSO4 4NH 3 5H 2O [Cu(NH3 ) 4 ]SO 4 .5H 2O

e.g., N H3 ,Cl — etc.

(The donor atom is oxygen)

(The donor atom is N)

Cr (NH 3)3 Cl3