Contents

Topic Page No.

Theory 01 - 12

Exercise - 1 13 - 24

Exercise - 2 25 - 32

Exercise - 3 33 - 38

Exercise - 4 39 - 40

Answer Key 41 - 49

Syllabus
Coordination compounds: nomenclature of mononuclear coordination compounds, colour
(excluding the details of electronic transitions) and calculation of spin-only magnetic moment;
cis-trans and ionisation isomerisms, hybridization
hybridization and geometries of mononuclea
mo nonuclearr coordination
coordinati on
compounds (linear, tetrahedral, square planar and octahedral).

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 COORDINATION COMPOUNDS

COORDINATION
COORDINATION COMPOUNDS
Coordination Compounds : Those addition compounds which retain their identity
(i.e. doesn’t lose their identity) in solution are called coordination compounds. For example, when KCN
solution is added to Fe(CN)2 solution, the species formed when dissolved in water no longer gives tests
of Fe2+ and CN.

Fe(CN)2 + 4KCN  !"  Fe(CN)

 ! 
2 . 4KCN or K4 [Fe(CN)6] (aq.) 4K+ (aq.) + [Fe(CN)6]4   (aq.)
 –

Various Terms Used in co ordination compounds :

Central Atom/Ion :
In a coordination entity –the atom/ion to which are bound a fixed number of ligands in a definite geometrical
arrangement around it, is called the central atom or ion. For example, the central atom/ion in the coordination
entities : [NiCl2(OH2)4], [CoCl(NH3)5]2+ and [Fe(CN)6]3  are Ni2+, Co3+ and Fe3+, respectively.
 –
respectively. These central
centr al
atoms / 
atoms  / ions
ions are also referred to as Lewis acids.
Ligands :
The neutral molecules, anions or cations which are directly linked with central metal atom or ion in the
coordination entity are called ligands.
 –
These may be simple ions such as Br , small molecules such as H 2O or NH3, larger molecules such
as H2NCH2CH2NH 2 or N(CH 2CH 2NH2)3 or even macromolecules such as proteins.

Coordination Number :
The coordination number of the central atom/ion is determined by the number of sigma bonds between
the ligands and the central atom/ions i.e. the number of ligand donor atoms to which the metal is directly
attached. Pi-bonds.

Some common co-ordination number of important metals are as given below.

Metal Coordination Number Metal Coordination Number

Cu+ 2, 4 Ni2+ 4, 6

Ag+ 2 Fe2+ 4, 6

Au+ 2, 4 Fe3+ 6

Hg22+ 2 Co2+ 4, 6

Cu2+ 4, 6 Co3+ 6

Ag2+ 4 Al 3+ 6

Pt 2+ 4 Sc 3+ 6

Pd2+ 4 Pt 4+ 6

Mg2+ 6 Pd4+ 6

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 COORDINATION COMPOUNDS

Table : Common Monodentate Ligands

Common Name IUPA C Name Formul a  

methy l is oc y anide met hy lis oc y anide CH3NC

t ripheny l ph
phos phine t ripheny l ph
phos phine/ t ripheny l ph
phos p
ph
hane P Ph 3
py ridine py ridine C 5H5N (py)
ammonia ammine NH3
met hy l amine met hy lamine MeNH2
wat er aqua or aquo H 2O
c arbony l c arbony l CO
t hioc arbony l t hioc arbony l CS
nit ros y l nit ros y l NO
 –
fluoro fluoro or fluorido* F
 –
c hloro c hloro or c hlorido* Cl
 –
bromo bromo or bromido* Br
 –
iodo iodo or iodido* I
 –
c y ano c y anido or c y anido-C* (C-bonded) CN
 –
is oc y ano is oc y anido or c y anido-N* (N-bonded) NC
 –
t hioc y ano t hioc y anat o-S(S-bonded) SCN
 –
is ot hioc y ano t hioc y anat o-N(N-bonded) NCS
 –
c y anato (c yanat e) c y anato-O (O-bonded) OCN
 –
iso
isocyan
cyanato (iso
isocya
cyanate)
te) cyan
cyanato-
to-N (N-bonded) NCO
 –
hy drox o hy droxo or hy droxido* OH
 –
nit ro nit rit o –N (N –bonded) NO2
nit rit o nit rit o –O (O –bonded) ONO  –

 –
nit rat e nit rat o NO3
 –
amido amido NH2
imido imido NH2  –

nit ride nit rido N3  –

 –
az ido az ido N3
 –
hy dride hy drido H
ox ide ox ido O2  –

perox ide perox ido O 22  –

 –
s uperox ide s uperox ido O2
 –
ac et at e ac et at o CH3COO
s ulphat e s ulphat o SO 42  –

t hios ulphat e t hios ulphat o S 2O32  –

s ulphite s ulphit o SO 32  –

 –
hy drogen s ulphit e hy drogensulphit o HSO 3
s ulphide s ulphido or t hio S2  –

 –
hy drogen s ulphide hy drogensulphido or merc apt o HS
 –
t hionit rit o t hionit rit o (NOS)
nit ros y lium nit ros ylium or nit ros onium NO+
nit ronium nit ronium NO 2+
* The 2004 IUPAC
IUPAC draft recomm
recommends
ends that anionic ligands will end with-ido.

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 COORDINATION COMPOUNDS

Table : Common Chelating Amines

Table : Common Multidentate (Chelating) Ligands

Co m m o n Na m e I UP A C N a m e A b b re vi a ti o n F o rm u l a S tru ctu r e

2,4-pentanediono  –
acetylacetonato a c ac CH3COCHCOCH3
or acetylacetonato

2 , 2'-b i p y ri di n e 2 , 2 '-b i py ri d y l bipy C10 H8 N2

1,10-phenanthroline/ 
1 , 10
10 -d i a m in
in o p h en a n t h re ne p h en , o-
o-p h e n C12 H8 N2
phenanthroline

o x a la t o ox alato ox C2 O 4 2
 –

 –
d i a l k y l d it h ioc a rb am a t o d i a l k y l c a rb a m o d i t h i o a t o dt c S2 CNR 2

1,2-ethanediylbis
1,2-bis(diphenylphophine)ethane d p pe P h2PC 2H 4PP h 2
(dipheylphosphene)

o-phenylenebis 1,2-phenylenebis
d i a rs C6 H4(As(CH 3)2)2
(dimethylarsine) (dimethylarsene)

butanedienedioxime  –
dimethylglyoximato DM G HO NC(CH 3 )C(CH3)NO
or dimethylglyoximato

O O
|| ||
1,2-ethanediyl —
O CH
CH 2C C H2C O —

 –  –
: :  
ethylenediaminetetraacetato (dinitrilo)tetraacetato E DTA ( OOCCH 2 )2 NCH 2 CH 2N(CH 2COO )2
or ethylenediaminetetraacetato —
O CH
CH 2C
|| C H2C|| O
—

O O

hydrotris-
pyrazolylborato
(pyrazo-1-yl)borato

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 COORDINATION COMPOUNDS

Nomenclature of Coordination Compounds

Writing the name of Mononuclear Coordination Compounds :
The following rules are followed when naming coordination compounds :

Names of the anionic ligands end in  –o. Anionic ligands ending with ‘ide’  are named by replacing ‘ide’
by suffix ‘ido ’.
e.g . Sym bol Name
N 3
 –
Nitrido
Cl ¯  Chlorido
O2 2  –
Peroxido
Br ¯ 
 ¯  Bromido
O2H ¯  Perhydroxido
CN ¯  Cyanido
S 2
 –
Sulphidido
O2 – Oxido
NH2  –
Amidido
OH ¯  Hydroxido
Ligands whose names end in ‘ite ’ or ‘ate ’  become ‘ito ’ or ‘ato’  i.e., by replacing the ending ‘e’
with ‘o’  as follows
  Sy
S ym bol Nam e as ligand
CO32 – Carbonato
C2O42 – Oxalato
SO42 – Sulphato
NO3 ¯  Nitrato
SO32 – Sulphito
CH3COO ¯  Acetato
NO2 ¯  (bon
(bonde
ded
d thr
throu
oug
gh oxy
oxyg
gen)
en) nit
nitri
rite
te (bon
(bondded thro
throu
ugh nitr
nitrog
ogen
en)) ni
nitro
tro
Neutral ligands are given the same names at the neutral molecules. For example. Ethylene diamine as
a ligand is named ethylene diamine in the complex. However some exceptions to this rule are
Aquo H2O
Ammine NH3
Carbonyl CO
Nitrosyl NO
Thiocarbonyl CS
tetraphosphorus P4
dioxygen O2
octasulphur S8
urea CO(NH2)2

Names of positive ligands ends in ‘ium ’  e.g.

NO+ Nitrosylium
NH2NH3+ Hydrazinium

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 COORDINATION COMPOUNDS

Prefixes mono, di, tri, etc., are used to indicate the number of the one kind of ligands in the
coordination entity.
entity. When the names of the ligands include a numerical prefix or are complicated
or whenever the use of normal prefixes creates some confusion, it is set off in parentheses
and the second set of prefixes is used.
2 di bis
3 tri t ris
4 tetra tetrakis
5 penta pentakis
6 hexa hexakis
7 hepta heptakis
Examples ; +
[CoCl2(NH2CH2CH2NH2)2] , dichloridobis(ethane-1,2-diamine)cobalt(III).
[NiCl2(PPh3)2], dichloridobis(tripheny
dichloridobis(triphenylphosphine)n
lphosphine)nickel(II).
ickel(II).
Oxidation state of the metal in cation, anion or neutral coordination entity is indicated by Roman
numeral in the parentheses after the name of metal.
If the complex ion is a cation, the metal is named same as the element. For example, Co
in a complex cation is called cobalt and Pt is called platinum. If the complex ion is an anion,
the name of the metal ends with the suffix - ate. For example, Co in a complex anion, [Co(SCN)4]2  –

is called cobaltate. For some metals, the Latin names are used in the complex anions.
ir o n ( F e ) ferrate lead (Pb) plumbate
silver (Ag) argentate t i n ( Sn ) stannate
gold (Au) aurate

Examples ; [Co(NH3)4Cl2]+, pentaamminechloridocobalt(III).

(NH 4)2 [Co(SCN)4], ammonium tetrathiocyanato-S-cobaltate(II).
tetrathiocyanato-S-cobaltate(II).
The neutral complex molecule is named similar to that of the complex cation.
Example ; [CrCl3(py)3], trichloridotris(pyridine)chromium(III).

BONDING IN COORDINATION COMPOUNDS :

Werner's Theory :
Alfred Werner (considered as the father of coordination chemistry) studied the structure of coordination
complexes such as CoCl3. 6NH3  and CuSO4. 4NH3  in 1893. According to him-
(a) Each metal in coordination compound possesses two types of valencies :
(i) prima
primaryry vale
valenc
ncyy or prin
princicipa
pall vale
valenc
ncie
ies
s or
or ioni
ionisa
sabl
ble
e val
valen
enci
cies
es..
(ii)
(ii) Seco
Second ndar
ary
y vale
valenc
ncy
y or noni
nonion
onisisab
able
le vale
valenc
ncie
ies
s
(b) Primary valencies are satisfied by anions only. only. The number
num ber of prim ary valencies depends upon the
oxidation state of the central metal. It may change from one compound to other. These are represented
by dotted lines between central metal atom and anion.
(c) Secondary valencies are satisfied only by electron pair donor, the ions or the neutral species. These
are represented by thick lines.
(d) Each metal has a fixed number of secondary valencies also referred as coordination number. The
coordination number depends mainly on the size and the charge on the central atom. The maximum
number of ions or molecules that the central atom can hold by secondary valencies is known as
coordination number.
(e) The ions attached to primary valencies possess ionising nature whereas the ions attached to secondary
valencies do not ionise when the complex is dissolved in a solvent.
(f) Every central ion tends to satisfy its primary as well as secondary valencies.
(g) The secondary valencies are directional and are directed in space about the central metal ion. The
primary valencies are non-directional. The presence of secondary valencies gives rise to stereoisomerism
in complexes.

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 COORDINATION COMPOUNDS

Effective Atomic Number Rule given by Sidgwick :

It can be defined as the resultant number of electrons with the metal atom
atom or ion after gaining electrons
electrons
from the donor atoms of the ligands.
Effective Atomic Number (EAN) = No. of electron present on the metal ato m/ion + No. of electrons
donated by ligands to it.
OR
Effective Atomic Number (EAN) = Atomic no. of central metal  –  Oxidation state of central metal
+ No. of electrons donated by ligands.
The complexes in which the EAN of the central atom equals the atomic number of the next noble gas,
are found to be extra stable.

Valence bond theory :

The salient features of the theory are summarised below.
(a) The central metal ion has a number of empty orbitals for accommodating electrons donated by the
ligands. The number of empty orbitals is equal to the coordination number of the metal ion for the particular
complex.
(b) The atomic orbitals (s, p or d) of the m etal ion hybridize to form hybrid orbitals with definite directional
properties. These hybrid orbitals now overlap with the ligand orbitals to form strong chemical bonds.
(c) The d-orbitals involved in the hybridization may be either inner (n  –1) d orbitals or outer n d-orbitals.
The complexes formed
f ormed in these two ways are referred to as low spin and high spin complexes,
com plexes, respectively.
respectively.
(d) Each ligand contains a lone pair of electrons.
(e) A covalent bond is formed by the overlap of a vacant hybridized metal orbital and a filled orbital of
the ligand. The bond is also sometimes called as a coordinate bond.
(f) If the complex contains unpaired electrons, it is paramagnetic in nature, while if it does not contain
unpaired electrons, it is diamagnetic in nature.

Co-ordination numbers, Hybridised orbitals and geometry of some co-ordination compounds

Coordination Hybridised orbital Geo met rical shape of Ex a m p l e s o f
N um be r t h e co m p l ex c o m p le x

2 sp [Ag(NH3)2]+
  Li
L i ne a r [Ag(CN)2 ¯ 
 ]¯ 

3 sp2 [Hg#3 ¯ 
 ]¯ 

4. s p3 [FeCl4 ¯ 
] ¯ 
[Ni(CO)4]0
Zn(NH3)4+2
[ZnCl4] 2,[CuX 4] 2
 –  –

where X = CN ¯ 
Cl ¯,Br¯,
 ¯,Br¯, # ¯, CNS
dsp 2

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 COORDINATION COMPOUNDS

The d-orbital involved is [Ni(CN)4] 2  –

4. dx2 y2  or
 –
orbital [Pt(NH3)4]+2
of the inner shell, i.e. it
is (n  – 1)d x2 y2 orbital
 –

dsp 3 [CuCl 5] 3
 –

5. T h e d - o r b i t a l is [MoCl5]0
(n - 1)dz2 or  o rbital [Fe(CO)5]0

sp3d
5. The d-orbital is ndx2 y2  –
[SbF5] 2 IF 5
 –

orbital

  Square pyramidal

d2sp 3
When d-orbitals are (n-1)
d-orbitals (Inner orbital [Cr(NH3)6+3]
6. complexes) or sp3d2 [Ti(H2O)6]+3
W hen d-orbitals are [Fe(CN)6] 2  –

nd orbital (Outer orbital [Co(NH3)6]+3

c o m p le x e s ) I n b o t h c a s e s [PtCl6] 2[CoF 6] 3
 –  –

p-orbitals are dz2  and dx2-y2

orbitals.

Octahedral

Crystal Field Theory :

The drawbacks of VBT of coordination compounds are, to a considerable extent, rem oved by the Crystal
Field Theory.
The crystal field theory (CFT) is an electrostatic model which considers the metal-ligand
metal-ligand bond to be ionic
arising purely from electrostatic interaction between the metal ion and the ligand. Ligands are treated as
point charges in case of anions or dipoles in case of neutral molecules. The five d orbitals is an isolated
gaseous metal atom/ion have same energy, i.e., they are degenerate. This degeneracy is maintained if
a spherically symmetrical field of negative charges surrounds the metal atom/ion. However, when this negative
field is due to ligands (either anions or the negative ends of dipolar molecules like NH3 and H2O) in a
complex, it becomes asymmetrical and the degeneracy of the d orbitals is lost. It results in splitting of
the d orbitals. The pattern of spitting depends upon the nature of the crystals field.

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 COORDINATION COMPOUNDS
Crystal field splitting in octahedral coordination entities :

Figure showing crystal field splitting in octahedral complex.

In general, ligands can be arranged in a series in the orders of increasing field strength as given below:
I < Br   < SCN < Cl < S2 < F < OH < C2O42 < H2O < NCS   < edta4 < NH3  < en < NO2 <
 –  –  –  –  –  –  –  –  –  –  –

 –
CN < CO
The two possibilites are :
(i) If $0 < P, the fourth electron enters one of the e g orbitals giving the configuration t 32geg1. Ligands for
which $0  < P are known as weak field ligands and form high spin complexes.
(ii) If $0 > P, it becomes more energetically favourable for the fourth electron to occupy a t 2g orbital with
configuration t2g4 eg0. Ligands which produce this effect are known as strong field ligands and form low
spin complexes.

Crystal field splitting in tetrahedral coordination entities :

Figure showing crystal field splitting in tetrahedral complex.

$t < $ o

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 COORDINATION COMPOUNDS
Crystal field splitting in square planar coordination entities :

$sp  = 1.3 $ o.

COLOUR IN COORDINATION COMPOUNDS :

Relationship between the wavelength of light absorbed and the colour observed In some coordination entitles
Table
 ––––––
 –––––––––
––––––
––––––
––––––
––––––
––––––
––––––
––––––
––––––
––––––
––––––
––––––
––––––
––––––
––––––
––––––
––––––
––––––
––––––
––––––
––––––
––––––
––––––
–––––––––
––––––––
––

Coordination entity Wavelen gth of li

light Colour of light Colo ur of co ordina tion
absorbed ( nm) absorbed entity
 ––––––
 –––––––––
––––––
––––––
––––––
––––––
––––––
––––––
––––––
––––––
––––––
––––––
––––––
––––––
––––––
––––––
––––––
––––––
––––––
––––––
––––––
––––––
––––––
––––––
–––––––––
––––––––
––

[CoCl(HN3)5]2+ 535 Yellow Vi o l e t

[Co(NH3)5(H2O)] 3+ 500 Blue Green Red

[Co(NH3)6]3+ 475 Blue Yellow Orange

[Co(CN)6]3- 310 Ultraviolet Pale Yellow

[Cu(H2O) 4]2+ 600 Red Bl u e

[Ti(H2O) 6]3+ 498 Yellow Gr een Purple

 ––––––
 –––––––––
––––––
––––––
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––––––
––––––
––––
–

ISOMERISM :
STRUCTURAL ISOMERISM :
(A) Ionisation is
isomerism :
This type of isomerism occurs when the counter ion in a coordination
coordination compound is itself a potential ligand
and can displace a ligand which can then become the counter ion. For example, following complexes
show ionisation isomerism.
[Co(NH3)5SO4]NO 3 and [Co(NH3)5NO 3]SO 4
[Co(NH 3)4(NO2)Cl]Cl and [Co(NH 3)4Cl2]NO2.
[Co(NH3)4(H 2O)Cl]Br2 and [Co(NH3)4BrCl]Br.H 2O. [Also an example of hydrate isomers.]
[Pt(NH3)4Cl2]Br 2, and [Pt(NH3)4Br2]Cl 2.
[CoCl(en) 2(NO2)]SCN, [Co(en)2(NO2)SCN]Cl and [Co(en)2(SCN)Cl]NO 2

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 COORDINATION COMPOUNDS
(B) Solva
lvate / hydra
drate isom
isome erism
rism :
It occurs when water forms a part of the coordination entity or is outside it. This is similar to ionisation
isomerism. Solvate isomers differ by whether or not a solvent molecule is directly bonded to the metal
ion or merely present as free solvent molecules in the crystal lattice. For example, CrCl 3 . 6H2O exists
in three distinct isomeric forms : [Cr(H2O)6]Cl3, violet ; [CrCl(H2O)5]Cl2.H2O, blue green : [CrCl2(H2O)4]Cl.2H2O,
dark green. These three cationic isomers can be separated by cation ion exchange from commercial CrCl3.6H2O.
A fourth isomer [Cr(H2O) 3Cl3], yellow green also occurs at high concentration of HCl. HCl. Apart from their
distinctive colours, the three isomers can be identified by the addition of excess of aqueous silver nitrate
to their aqueous solutions, which precipitates chloride in the molar ratio of 3 : 2 : 1 respectively.respectively.
Complex Reaction with AgNO3 Reaction with conc. H2SO4(dehydrating agent)
[Cr(H2O)6]Cl3 in the
the mo
mola
larr rat
ratiio of
of 3:
3:1 No wate
waterr mol
molecul
eculee is
is los
lostt or
or no
no rea
react
ctio
ionn
[CrCl(H2O)5]Cl2.H2O in the molar raratio of 2:
2:1 one mo
mole of wa
water is lolost per momole of
of co
com pl
plex
[CrCl2(H2O)4]Cl.2H2O in th the mo
molar raratio
tio of
of 1:
1:1 two mo
mole of water arare lost per mo molle of
of cco
omp
mpllex
Other examples are :
[Co(NH3)4(H2O)Cl]Cl2 and [Co(NH3)4Cl2]Cl.H2O
[Co(NH3)5(H2O)](NO3)3 and [Co(NH3)5(NO3)](NO3)2.H2O.
(C) Linkage isomerism :
In some ligands, like ambidentate ligands, there are two possible coordination sites. In such cases, linkage
isomerism exist. e.g.,NO2 group can be bonded to metal ions through nitrogen ( –NO2) or through oxygen
( –ONO). SCN too can be bonded through sulphur ( –SCN) thiocyanate or through nitrogen ( –NCS)
isothiocyanate.
For example : :  [Co(ONO)(NH3)5] Cl2  & [Co(NO2) (NH 3)5] Cl2 .
(D) Coord inatio n isomerism :
Coordination compounds made up of cationic and anionic coordination entities show this type of isomerism
due to the interchange of ligands between the cation and anion entities. Some of the examples are :
(i) [Co(NH3)6][Cr(CN) 6] and [Cr(NH3)6](Co(CN) 6]
(ii) [Cu(NH3)4][PtCl4] and [Pt(NH3) 4][CuCl4]
(iii) [Co(NH3)6][Cr(SCN)6] and [Cr(NH3)4(SCN)2][Co(NH3)2(SCN)4]
(iv) [Pt(NH3)4][PtCl6] and [Pt(NH3)4Cl2][PtCl4]
Such isomers are expected to have significant differences in their physical and chemical properties.
(E) Ligand isomerism :
Since many ligands are organic compounds which have possibilities for isomerism, the resulting com plexes
can show isomerism from this source.
For example ; ligands 1,2-diaminopropane(propylenediamine or pn) an
pn)  andd
1,3-diaminopropane(trimethylenediamine or tn)
tn) are such pairs. Sim ilarly ortho-, meta- and para-toluidine
(CH3C6H4NH2).

(F) Polymerisation is
isomerism :
Considered to be a special case of coordination isomerism, in this the various isomers differ in formula
weight from one another,
another, so not true isomers in real sense. For example [Co(NH3)4(NO2)2][Co(NH 3)2(NO2)4],
[Co(NH 3) 6][Co(NO 2) 6], [Co(NH 3 ) 5(N O 2 )][Co(NH 3) 2 (N O 2) 4 ] 2 , [Co(NH 3) 6][Co(NH 3 ) 2(N O 2 ) 4 ] 3 ,
[Co(NH3)4(NO 2)2]3[Co(NO2)6] and [Co(NH3)5(NO 2)2]3[Co(NO2)6]2. These all have the empirical formula
Co(NH3)3(NO 2)3, but they have formula weights that are 2,2,3,4,4 and 5 times this, respectively.

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 COORDINATION COMPOUNDS

Stereoisomerism

Geometrical Isomerism
This type of isomerism arises in heteroleptic complexes due to different possible geometric arrangements
of the ligands. Geometrical isomerism is common among coordination compounds with coordination numbers
4 and 6.
Coordination Number Four :
Tetrahedral Complex :
The tetrahedral compounds can not show geometrical isomerism as we all know that all four positions
are equivalent in tetrahedral geometry.
Square Planar Complex :
In a square planar complex of formula [Ma2b2] [a and b are unidentate], the two ligands ‘a’ may be arranged
adjacent to each other in a cis isomer, or opposite to each other in a trans isomer as depicted.

Coordination Number Six :

Geometrical isomerism is also possible in octahedral complexes.

Optical Isomerism :
A coordination compound which can rotate the plane of p olarised light is said to be optically active.
When the coordination compounds have same formula but differ in their ability to rotate directions
of the plane of polarised light are said to exhibit optical isomerism and the molecules are optical
isomers. Optical isomers are mirror images that cannot be superimposed on one another. These are
called as enantiomers.
Octahedral complex :
Optical isomerism is common in octahedral complexes involving didentate ligands. For example,
[Co(en)3] 3+   has d and !   forms as given below.

d and !   of [Co(en) 3 ] 3+
Cis-isomer of [PtCl 2(en)2]2+ show optical isomerism as shown below because of the absence of plane
of symmetry as well as centre of symmetry.

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 COORDINATION COMPOUNDS

d and !   of cis-[PtCl 2(en) 2] 2+

(e n2)] 2+   does not show optical isomerism.
But trans isomer of [PtCl 2(en

Tetrahedral complex :
Optical isomerism is expected in tetrahedral complexes of the type [Mabcd] analogous to tetrahedral
carbon atom.

Organometallic compounds :
Bonding in Metal Carbonyls
The metal –carbon bond in metal carbonyls possess both s and p character. The M—C % bond is formed
by the donation of lone pair of electrons on the carbonyl carbon (CO is a weak base) into a vacant orbital
of the metal. The M — C & bond is formed by the donation of a pair of electrons from a filled d orbital
of metal into the vacant antibonding &* orbital of carbon monoxide. Thus carbon monoxide acts as % donor
(OC " M) and a & acceptor (OC ' M), with the two interactions creating a synergic effect which strengthens
the bond between CO and the metal as shown in in figure.

(
&
&

%
 "
M    " C O
 "
   "
&

Synergic bonding
(i) As M — C & bonding increases, the C — O bond becomes weaken. The greater the positive charge
on the central metal atom, the less readily the metal can donate electron density into the &* orbitals of
the carbon monoxide ligands to weaken the C —  O bond.
(ii) In contrast, in the anionic complex (i.e. carbonylate anion) the metal has a greater electron density
to be dispersed, with the result that M — C & bonding is enhanced and the C — O bond is diminished
in strength. For example ; in isoelectronic complexes the strength of metal-ligand bond increases and
strength of C — O bond in CO decreases (because bond order decreases) as the negative charge on
the complexes increases.
Thus order of CO bond strengths ;
(a) [M(CO)6]+  > [Cr(CO)6] > [V(CO)6]   > [Ti(CO)6]2 . (b) [N
 –  –
[Ni(CO)4] > [Co(CO)4]   > [Fe(CO)4]2 .
 –  –

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 COORDINATION COMPOUNDS

PART - I : OBJECTIVE QUESTIONS

* Marked Questions are having more than one correct option.

SECTION (A) : INTRODUCTION OF COORDINATION COMPOUNDS
A-1. Some salts although containing two different metallic
m etallic elements give test for one of them in solution. Such salts are :
(A) complex salt (B) double salt (C) normal salt (D) none

A-2. All ligands are :

(A) Lewis acids (B) Lewis bases (C) neutral (D) none

A-3. Diethylenetriamine is :
(A) chelating agent (B) tridentate neutral molecule
(C) tridentatemonoanion (D) (A) and (B) both
A-4. In brown ring complex compond [Fe(H2O)5NO]SO4, the oxidation state of Fe is :
(A) + 2 (B) + 3 (C) + 4 ( D) + 1
A-5. In the complex [CoCl2(en)2]Br, the co-ordination number and oxidation state of cobalt are :
(A) 6 and +3 (B) 3 and +3 (C) 4 and +2 (D) 6 and +1
A-6. What is the charge on the complex [Cr(C2O4)2(H2O)2] formed by Cr(!!!) ?
(A) +3 (B) +1 (C) + 2 (D) –1
A-7. Which of the following are bidentate monoanion ligands
ligands ?
(1) Acetylacetonato (2) Oxalato ion (3) Dimethylglyoximato
Select the correct answer using the codes given below :
(A) 1 only (B) 1 and 3 only (C) 3 only (D) 2 and 3 only

A-8. Match the following

f ollowing
Column- Column-

(a) en (p)

(b) dmg (q)

(c) EDTA (r)

(d) gly

(e) ox (s)

(t)

(a) (b) (c) (d) (e) (a) (b) (c) (d) (e)
(A) r p t q s (B) r p t q s
(C) p s q r t (D) s q t p r

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 COORDINATION COMPOUNDS

A-9. The donor sites of (EDTA)4  are ?

 –

(A) O atoms only (B) N atoms only

(C) Two N atoms and four O atoms (D) Three N atoms and three O atoms

SECTION (B) : IUPAC NOMENCLATURE OF COORDINATION COMPOUNDS

B-1. The IUPAC name of [CoCl(NO2)(en)2] Cl is  –

(A) Chloridonitrito-
Chloridonitrito-O-bis(ethylen
O-bis(ethylene
e diammine)co
diammine)cobalt
balt (III) chlori
chl oride
de
(B) Chloridonitrito- N-bis(ethylene
N-bis(ethylene diammine)cobalt
diammine)cobalt (II) chlori
chl oride
de
(C) Chloridobis(ethane-1,2-diamine)nitrito-N-cobalt(III) chloride
(D) Bis(ethylene diammine) chloridonitrito-N-cobalt(III) chloride

B-2. IUPAC name of [Pt(NH3)3(Br)(NO2)Cl]Cl is  –

(A) Triamminechloridobromonitrito-N-platinum (IV) chloride
(B) Triamminebromonitrito-N-chloridoplatinum (IV) chloride
(C) Triamminebromidochloridon
Triamminebromidochloridonitrito-N-plat
itrito-N-platinum(IV)
inum(IV) chloride
(D) Triamminenitrito-N-chloridobromidoplati
Triamminenitrito-N-chloridobromidoplatinum
num (IV) chloride

B-3. The IUPAC name for [Co(NCS)(NH 3)5]Cl2 is  –

(A) Pentaamminethiocyanato-N-cobalt(III) chloride
(B) Pentaamminethiocyanato-S-cobalt(III) chloride
(C) Pentaamineisothiocyanato-N,S-cobalt(III) chloride
(D) Pentaammine
Pentaammine (mercapto-N) cobalt(III) chloride

B-4. The correct IUPAC name of the complex Fe(C5H5)2 is  –

(A) Cyclopentadienyliron(II) (B) Bis(cyclopentadienyl)iron(II)
(C) Dicyclopentadienylferrate(II) (D) Ferrocene

B-5. The formula of the complex tris(ethane-1

tris(ethane-1,2-
,2- diamine)cobalt(III)
diamine)cobalt(III) sulphate is –
(A) [Co(en)2SO4] (B) [Co(en)3SO4] (C) [Co(en)3]SO4 (D) [Co(en)3]2(SO4)3

B-6. The IUPAC

IUPAC name of Fe(CO)5 is  –
(A) Pentacarbonylferrate (0) (B) Pentacarbonylferrate(III)
(C) Pentacarbonyliron (0) (D) Pentacarbonyliron(II)

B-7. K3[Fe(CN)6] is  –
(a) Po
Potassium he
hexacynoferrous(III) (b) Po
Potassium he
hexacynoferrate(III)
(c) Potassium ferricyanide (d) Hexacyano ferrate(III) potassium
Correct answer is  –
(A) Only (a) an
and (b) (B) On
Only (b) an
and (c
(c) (C) Only (a) and (c) ( D ) On l y ( b ) a n d ( d )

B-8. The IUPAC name of the complex [CrCl

[CrC l2(H2O)4]NO3 is  –
(A) Dichlo
Dichlorid
ridote
otetra
traaqu
aquach
achrom
romium(
ium(II
III)
I) nit
nitrat
rate
e (B) Tetraaq
etraaquad
uadich
ichlo
lorid
ridoch
ochromi
romium(I
um(III)
II) nitra
nitrate
te
(C) Chromiumtetraaquadichloridonitrate (D) Dichloridotetraaquachromium(II)
Dichloridotetraaquachromium(II) nitrate

B-9. The chloro-bis (ethylenediamine)

(ethylenediamine) nitro cobalt(III) ion is –
(A) [Co(NO2)2(en)2Cl2]+ (B) [CoCl(NO2)2(en)2]+ (C) [Co(NO2)Cl(en)2]+ (D) [Co(en)Cl2(NO 2)2]  –

B-10. A complex anion is formed by Osmium (in some oxidation state) with ligands (in proper number so that coordination
number of osmium becomes six). W hich of the following can be its correct IUPAC
IUPAC name?
(A) pe
pentachloridonitridoosmium(VI) (B) pe
pentachloridonitridoosmate(VI)
(C) azidopentachloridoosmate(VI) (D) None of these

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 COORDINATION COMPOUNDS

B-11. Complex ion [ FeN3(O2)(SCN)4]4 is named as : (coordination number of central

 –
c entral metal ion in complex is six)
(A) azidosuperoxidotetrathiocyanato-S-ferrate(II) (B) azidod
azidodiox
ioxyg
ygente
entetra
trathi
thiocy
ocyana
anatofe
toferrat
rrate(
e(III)
(C) azidoperoxidotetrathiocyanato-S-ferrate(
azidoperoxidotetrathiocyanato-S-ferrate(II) (D)
(D) azid
azidod
odio
ioxi
xido
dote
tetra
trath
thio
iocy
cyan
anat
ato-S
o-S-fe
-ferr
rrat
ate(
e(III)

B-12. Trioxalatoaluminate(III) and tetrafluoro-borate(III) ions are:

(A) [Al(C2O4)3] , [BF4]3 –
(B) [Al(C2O4)3]3+ , [BF4]3+
(C) [Al(C2O4)3]3  , [BF4]
 –  –
(D) [Al(C2O4)3]2  , [BF4]2
 –  –

B-13. The correct IUPAC name for the compound [Co(NH3)4CI(ONO)]Cl is :

(A) Tetraamminechloridonitrito
etraamminechloridonitrito-N-cobalt(III)chloride
-N-cobalt(III)chloride
(B) Chloridonitrito-O-tetraamminecobalt(II) chloride
(C) Dichloridonitrito-O-tetraamminecobalt(III)
Dichloridonitrito-O-tetraamminecobalt(III)
(D) Tetraamminechloridonitrito-O-cobalt(II
etraamminechloridonitrito-O-cobalt(III)
I) chloride

B-14. A complex cation is formed by Pt (in some oxidation state) with ligands (in proper number so that coordination
number of Pt becomes six). Which of the following can be its
its correct IUPAC
IUPAC name :
(A) Diammineethylenediaminedithiocyanato-S-platinum (II) ion
(B) Diammineethylenediaminedithiocyanato-S-platinate (IV) ion
(C) Diammineethylenediaminedithiocyanato-S-platinum (IV) ion
(D) Diamminebis (ethylenediamine)
(ethylenediamine) dithiocyanate-S-
dithiocyanate-S- platinum (IV) ion

SECTION (C) : WARNER’S COORDINATION THEORY AND EXPERIMENTAL

  METHODS TO DETERMINE STRUCTURE OF COORDINATION COMPOUNDS

C-1. When AgNO3 is added to a solution of Co(NH3)5Cl3, the precipitate of AgCl shows two ionisable
ionisable chloride
ions. This means that-
(A) two chlorine atom satisfy primary valency and one secondary valency.
(B) one
one chlorine
chlorine atom satisfies primary as well as secondary valency.
valency.
(C) three chlorine atoms satisfy primary valency.
valency.
(D) three chlorine atoms satisfy secondary valency.
valency.

C-2. A co-ordinati
co-ordination
on complex
complex of cobalt
cobalt has
has molecular
molecular formula
formul a containing
containin g five ammonia
am monia molecules,
molecule s, one nitro
ni tro group
and two chlorine
chlorin e atoms for one cobalt atom.
ato m. One mole
mol e of this compound
com pound produc
produces
es three
three mole
mole ions
ions in an
aqueous solution. In reacting this solution with excess of silver nitrate solution, two moles of AgCl get precipitated.
The ionic formula of this complex would be  –
(A) [(Co(NH3)4.NO2Cl].[(NH3)Cl] (B) [(Co(NH3)5Cl].[Cl(NO2)]
(C) [(Co(NH3)5(NO2)]Cl2 (D) [(Co(NH3)5].[(NO2)2Cl2]

C-3. Which of the following complex will give white precipitate with barium chloride solution ?
(A) [Cr(NH3)5Cl]SO4 (B) [Cr(NH3)SO4]Cl (C) [Co(NH3)6]Br3 (D) None of these

C-4. Give the correct increasing order of electrical conductivity of aqueous solutions of following complex entities.
I. [Pt(NH3)6]Cl 4 II. [Cr(NH
[Cr(NH3)6]Cl3 III.
III. [Co(NH
[Co(NH3)4Cl2]Cl IV. K2[PtCl6]
(A) III < IV < II < I (B) IV < II < III < I (C) II < I < IV < III ( D ) I < I I < I V < II I

C-5. When potassium hexachloroplatinate

hexachloroplatinate (II) is dissolved in water.
water. The solution  –
(A) contains 6 ions per molecule (B) reacts with AgNO3 to give 6 moles of AgCl
 –
(C) does not contain any Cl  io
 ion (D) contains K+, Pt4+ and Cl  ions –

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 COORDINATION COMPOUNDS

C-6. Consider the following statements.

According the Werner's
W erner's theory,
theory,
(1) ligands are connected to the metal ions by ionic bonds.
(2) secondary valencies have directional properties.
(3) secondary valencies are non-ionisable.
Of these statements :
(A) 1, 2 and 3 are correct (B) 2 and 3 are correct
(C) 1 and 3 are correct (D) 1 and 2 are correct

C-7. A compound is made by mixing cobalt(III) nitrite and potassium

potassium nitrite solutions in the ratio of 1 : 3. The aqueous
solution of the compound
com pound showed 4 particles per molecule
m olecule whereas molar conductivity reveals the presence of
six electrical charges. The formula of the compound is :
(A) Co(NO2)3 . 2KNO2 (B) Co(NO2)3 . 3KNO2 (C) K3[Co(NO2)6] (D) K[Co(NO2)4]

C-8. Which of the following will exhibit maximum ionic conductivity?

(A) K4 [Fe(CN6] (B) [Co(NH3)6] Cl3 (C) [Cu(NH3)4] Cl2 (D) [Ni (CO)4]

C-9. A co-ordination complex has the formula PtCl4.2KCl. Electrical conductance measurements indicate the presence
of three ion in one formula
form ula unit. Treatment with AgNO3 produces no precipitate of AgCl. What is the co-ordination
co-ord ination
number of Pt in this complex ?
(A) 5 (B) 6 (C) 4 (D) 3

C-10. The complex [Cr(H2O)4Br2]Cl gives the test for :

(A) Br –
(B) Cl  –
(C) Cr3+  –  –
(D) Br  and Cl  both

C-11. How many moles of AgCl would be obtained, when 100 ml of 0.1 M Co(NH3)5Cl3 is treated with excess of
AgNO3?
(A) 0.01 (B) 0.02 (C) 0.03 (D) none of these

C-12. Concentrated H2SO4 will not dehydrate the following complex :

(A) [Cr(H2O)5Cl]Cl2.H2O (B) [Cr(H2O)4Cl2]Cl.2H2O
(C) [Cr(H2O)6]Cl3 (D) all of these

C-13. On adding AgNO3 solution to a solution of [Pt(NH3)3Cl3]Cl, the percentage of total chloride ion precipitated is:
(A) 100 (B) 75 (C) 50 (D) 25

C-14. W erner’s representation is :

CoCl3.4H2O is an anhydrous binary solute hence its Werner

(A) (B) (C) (D) none

SECTION (D) : VALENCE BOND THEORY

D-1. Which of the following statements is correct for complex [Cr(NH3)(CN)4(NO)]2 (given that n = 1)?
 –

(A) It is d2sp3 hybridised .
(B) The chromium is in + 1 oxidation
oxidation state.
(C) It is heteroleptic complex and its aqueous solution
solution is coloured.
(D) All of these.

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 COORDINATION COMPOUNDS
D-2. Match the geometry given in column A with the complex given in column B using the codes given below :
Co lu mn (A) Co l u mn ( B )
i) Tetrahedral (a) [Cu(NH3)4]2+
ii) Octahedral (b) [Ag(NH3)2]+
i ii) Square planar ( c) Fe(CO)5
iv) Trigonal bipyramidal (d) [Cr(H2O)6]3+
v) Linear (e) [NiCl4]2 –
(A)
(A) (i)-(e
-(e), (ii
(ii)-(
)-(d), (iii)-(a
-(a), (iv
(iv)-(c) ,(v)-(b
)-(b)) (B) (i)-(d),
(d), (ii)-(e
-(e), (ii
(iii)-(
)-(a), (iv)-(c)
(c) ,(v)
(v)-(b
-(b)
(C) (i)-(d), (ii)-(e), (iii)-(b), (iv)-(a) ,(v)-(c) (D) (i)-(c), (ii)-(e), (iii)-(b), (iv)-(a) ,(v)-(d)

D-3. Match the following using the codes given below :

1. Double salt (a) [Co(NH3)3Cl3]
2. Z e is e ' s s a lt (b) Hexadentate
3. Neutral m olecule ( c) b i d en t a t e
4. EDTA (d) P a r a m a gn e t i c
5. Ni(CO)4 (e) FeSO4.(NH4)SO4.6H2O
3+
6. [Cr(NH3)6] (f) K4Fe(CN)6
7. L ow s p in c o m p le x (g) Diam agnetic
8. Glycine (h) An organometallic compound
(A) (1 –e); (2 –h); (3 –a); (4 –b); (5 –g); (6 –d); (7 –f); (8 –c).
(B) (1 –h); (2 –e); (3 –a); (4 –b); (5 –g); (6 –d); (7 –f); (8 –c).
(C) (1 –h); (2 –e); (3 –a); (4 –b); (5 –d); (6 –g); (7 –c); (8 –f).
(D) (1 –h); (2 –a); (3 –e); (4 –b); (5 –d); (6 –g); (7 –f); (8 –c)

SECTION (E) : CRYSTAL

 CRYSTAL FIELD THEORY
T HEORY AND ITS APPLICATION
APPLICATIONSS
E-1. The number of unpaired electrons in d6, low spin, octahedral complex is :
(A) 4 (B) 2 (C) 1 (D) 0

E-2. Low spin complex is formed by :

(A) sp3d2 hybr
 hybrid
idiizati (B) sp3d hybridization
ation (B) (C) d2sp3 hyb
(C)  hybrid
ridiza
ization
tion (D) sp3 hybridization
(D)

E-3. The number of unpaired electrons present in complex ion [FeF6]3- is :

(A) 5 (B) 4 (C) 6 (D) 0

E-4. The crystal field splitting energy for octahedral complex (!o) and that for tetrahedral complex (!t ) are related as:
4 9
(A) !t = !0 (B) !t = 0.5 !o (C) !t = 0.33 !o (D) !t = !0
9 4

E-5. The complex [Pt(NH3)4]2+ has ..... structure :

(A) square planar (B) tetrahedral (C) pyramidal (D) pentagonal

E-6. What is the shape of Fe(CO)5 molecule ? Given that its dipole moment = 0.
(A) Tetrahedral (B) Octahedral (C) Trigonal bipyramidal (D) Square pyramidal

E-7. Which of the following is a high spin complex ?

(A) [Co(NH3)6]3+ (B) [Fe(CN)6]4 – (C) [Ni(CN)4]2 – (D) [FeF6]3 –

E-8. Which has maximum paramagnetic nature ?

(A) [Cu(H2O)4]2+ (B) [Cu(NH3)4]2+ (C) [Mn(H2O)6]2+ (D) [Fe(CN)6]4 –

E-9. Which of the following

f ollowing complexes has a geometry different from others ?
2 –
(A) [Ni Cl4] (B) Ni (CO)4 (C) [Ni(CN)4]2 – (D) [Zn(NH3)4]2+

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 COORDINATION COMPOUNDS

E-10. Select the correct statement.

(A) Complex ion [MoCl6]3  is
 is pa  –
paramagnetic. (B) Co
Complex io [Co(en)3]3+ is diamagnetic.
ion [C
(C) Both (A) and (B) are correct. (D) None of these is correct.

E-11. Amongst Ni(CO)4, [Ni(CN)4]2  and NiCI42 :  –  –

(A) Ni(CO)4 and NiCI42 are diamagnetic and [Ni(CN)

 –
[Ni(CN)4]2  is paramagnetic.  –

 –  –
(B) NiCI42 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 NiCI42 is paramagnetic.
 –
paramagnetic.  –

2 2  –
(D) Ni(CO)4 is diamagnetic and, NiCI4  and [Ni(CN)4]  are paramagnetic.  –

SECTION : (F) STABILITY

STABILITY IN COORDINATION
COORDINATION COMPOUNDS
COM POUNDS
F-1. In complexes more
m ore stability is shown by :
(A) [Fe(H2O)6]3+ (B) [Fe(CN)6]3  –
(C) [Fe(C2O4)3]3  –
(D) [Fe(Cl)6]3
 –

F-2. From the stability

s tability constant
constant (hypothetical values), given below,
below, predict which is the most stable complex ?
(A) Cu  + 4NH3  # 
2+  #$  [Cu(NH3)4]  , K = 4.5 × 10
2+ 11

(B) Cu2+ 4CN  #  – #$  [Cu(CN)4]2 , K = 2.0 × 1027

 –

(C) Cu2+ + 2en  # 

 #$  [Cu(en)2]2+ , K = 3.0 × 1015
(D) Cu2+ + 4H2O  # 
 #$  [Cu(H2O)4]2+, K = 9.5 × 108

F-3. Which of the following statements is incorrect ?

(A) The stability constant of [Co(NH3)6]3+ is greater than that of [Co(NH3)6]2+.
 –  –  –  –  –
(B) Among F , Cl , Br  and I , F  forms strongest complexes due to small sm all size.
2+ 2+
(C) [Cu(NH3)4]  is thermodynamically more stable than [Zn(NH3)4] .
(D) Among [Fe(CN)6]3 , [Fe(H2O)6]2+ and [Fe(en)3]3+, [Fe(CN)6]3  is most stable.
 –  –

SECTION : (G) : ISOMERISM IN COORDINATION

COORDINATION COMPOUNDS
G-1. Which of the following is pair of ionization
ionization isomers ?
(A) [Co(NH3)5Br]SO4 and [Co(NH3)5SO4]Br
(B) [Cr(H2O)5Cl]Cl2.H2O and [Cr(H2O)4.Cl2]Cl.2H2O
(C)[Co(NH3)6]Cr(CN)6 and [Cr(NH3)6][Co(CN) 6]
(D) cis-[Pt(NH3)2Cl2] and tran-[Pt(NH3)2Cl2]

G-2. In coordination compounds, the hydrate isomers differ :

(A) In the number of water molecules of hydration only.
on ly.
(B) In the number of water molecules onlyonly present as ligands.
(C) Both (A) and (B).
(D) In their coordination
coordination number of the metal atom.

G-3. Which one of the following octahedral complexes will not show geometrical
geometrical isomerism
(A and B are monodentate ligands)
ligands) ?
(A) [MA5B] (B) [MA2B4] (C) [MA3B3] (D) [MA4B2]

G-4. cis-trans-isomerism
cis-trans- isomerism is found in square planar complexes of the molecular formula (a and b are monodentate
ligands)  –
(A) Ma4 (B) Ma3b (C) Ma2b2 (D) Mab3

G-5. Which would exhibit co-ordination isomerism ?

(A) [Cr(NH3)6][Co (CN)6] (B) [Co(en)2Cl2]+
(C) [Cr(NH3)6][Cl 3 (D) [Cr(en)2Cl2]+

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G-6. [Co(NH3)5Br] SO4 and [Co(NH3)5SO4] Br are...................... isomers.

(A) Linkage (B) Geometrical (C) Ionization (D) Optical

G-7. Which of the following is not optically active ?

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

G-8. A complex shown below : A

(A) exhibits optical isomerism only F B
(B) exhibits geometrical isomerism only
M
(C) exhibits both optical and geometrical isomerism
(D) none E C
D
G-9. The phenomenon of optical activity will
will be shown by ?
A en
A
B B A A B

(A) M (B) M en (C) en M en (D) M

B B B B
B A en
A

G-10. A square planar complex represented as it will show which isomerism ?

NH2  NH2
 CH2  CH2

 CH2  CH2
 H2N  H2N

(A) Geom etrical isom erism (B) Optical isomerism

(C) Linkage isom erism (D) None

G-11. The complexes given below are :

en
A
A

en M en M

A
A en
(A) geometrical isomers (B) position isomers
(C) optical isom ers (D) identical

G-12. Theoretically the number

number of geom etrical isomers expected for octahedral complex [Mabcdef] is :
(A) Zero (B) 30 (C) 15 (D) 9

G-13. The complexes [Pt(NH3)4] [PtCl6] and [Pt(NH3)4Cl2] [PtCl4] are :

(A) linkage isomers (B) optical isomers
(C) co-ordination isomers (D) ionisation isomers

G-14. Which of the following complexes show geometrical as well as optical isomerism ?
(1) [Cr(OX)3]3  –
(2) [Rh(en)2Cl2]+ (3) [Co(NH3)2(Cl)2(en)]+
(A) 1 only (B) 1 and 2 only (C) 2 and 3 only (D) All 1, 2, 3

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SECTION (H) : EAN RULE AND ITS APPLICATIONS IN METAL CARBONYLS

H-1. The EAN of metal atoms in [Fe(CO)2(NO+)2] and Co2(CO)8 respectively are :
(A) 34, 35 (B) 34, 36 (C) 36, 36 (D) 36, 35

H-2. The EAN of platinum in potassium hexachloridoplatinate(IV)

hexachloridoplatinate(IV) is:
(A) 90 (B) 86 (C) 76 (D) 88

H-3. In which of the following pair the EAN of central metal atom is same?
(A) [Fe(CN)6]3  and [Fe(CN)6]4
 –  –
(B) [Cr(NH3)6]3+ and [Cr(CN)6]3  –

(C) [FeF6]3  and [Fe(CN)6]4

 –  –
(D) [Ni(CO)4] and [Ni(CN)4]2  –

H-4. EAN of a metal carbonyl M(CO)x is 36. If atomic number of metal M is 26, what is the value of x ?
(A) 4 (B) 8 (C) 5 (D) 6

H-5. Following Sidwick's rule of EAN, Co(CO) x will be :

(A) Co2(CO)4 (B) Co2(CO)3 (C) Co2(CO)8 (D) Co2(CO)10

SECTION (I) : SOME IMPORTANT COORDINATION COMPOUNDS

I-1. Which of the following statements is correct ?

(A) Chlorophyll contains magnesium metal.
(B) Wilkinson catalyst is used for the hydrogenation of alkenes .
(C) Metal carbonyls possess both % and & bonds.
(D) All of these .

I-2. Which of the following is correct for the Zeise’s salt ?

(A) The complex ion is square planar.
planar.
(B) The central metal ion, platinum is in + 2 oxidation state.
(C) H2C = CH2 molecules is perpendicular to the PtCl3 plane
(D) All of these.

I-3. Which amongst the following are organometallic compounds ?

1. Al2(CH3)6 2. K[PtCl
K[PtCl3C2H2] 3. N(CH3)3
(A) 1 only (B) 3 only (C) 1 and 2 only (D) 1, 2 and 3

I-4. In Ziesses salt C = C bond length is :

-'C 0 C bond length in ethane is 1.54Å *

'
Note : ,C / C bond length in ethene is 1.34Å )
'+C . C bond length in ethyne is 1.20Å '
(
(A) 1.37 Å (B) 1.19 Å (C) 1.87 Å (D) 1.34 Å

I-5. Which is not a &-bonded complex ?

(A) Zeise's salt (B) Ferrocene
(C) bis(benzene) chromium (D) Tetraethyl lead

I-6. What is wrong about the compound K [Pt (12  – C2H4) Cl3] ?
(A) It is called Zeise's salt. (B) It is & bonded complex.
(C) Ox
Oxidation nu number of
of Pt
Pt is
is +4
+4. (D) Four ligands surround the platinum atom.

I-7. Formula of ferrocene is:

(A) [Fe(CN)6]4  –
(B) [Fe(CN)6]3+ (C) [Fe(CO)5] (D) [Fe(C5H5)2]

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PART - II : MISCELLANEOUS QUESTIONS

COMPREHENSION
Comprehension # 1

Read the following passage carefully and answer the questions.

Splitting energy ("0) can usually be measured from the absorption spectra of the complex ions. In simple cases
when light is absorbed by a complex ion, an electron in one of the lower energy orbitals is excited to one of the
higher energy orbital. The energy corresponding to the frequency of absorbed light is equal to "0. If value of "0 for
the complex is in visible region, the complex is coloured and the value of "0 lies in ultraviolet or infrared region,
the complex is colourless. For octahedral complexes the crystal field stabilisation energy is given by CFSE = [ –  –

0.4 t2gN + 0.6 egN1] "0 where N and N1 are number of electrons in t2g and eg orbitals respectively.
The values of CFSE can be used for the correction of the experimental
experim ental values of heats of hydration of divalent
ions of first row transition metals.
m etals. The correction value can be obtained by substracting the calculated CFSE
values from the experimental values.

1. The value of crystal field splitting ("0) for [Ti(H2O)6]3+ is 243 kJ mol 1. The crystal field stabilization energy
 –

(CFSE) in this complex is : (in kJ mol 1).  –

3 2 2
(A) × 243 (B) × 243 (C) 3 × × 243 (D) 243
5 5 5

2. Which of the following statements is correct ?

(A) Zinc(II) ion has a zero CFSE for any geometry.
(B) A solution of [Ti(H 2O)6]3+ is purple as the value of " for the H2O complex is in the visible region.
(C) Solutions of [Fe(CN)6]4  and [Fe(H2O)6]2+ appear colourless in dilute solutions.
 –

(D) All of these.

3. The heat of hydration of Cr2+ ion is 460 k cal/mole. For [Cr(H2O)6]2+, "0 = 13,900 cm 1. What heat of hydration
 –

would be, if there were no crystal field stabilisation energy ?

(A)  – 436 k cal/mole (B)  – 245 k cal/mole (C)  – 4.84 k cal/mole (D) none of these

Comprehension # 2

In metal carbonyls , there is synergic bonding interaction between metal and carbon monoxide .This leads to
increase in strength of metal
m etal ligand bond and decrease in bond order of CO in carbonyl complex as compared
to bond order in carbon monoxide.
m onoxide.
Simple carbonyls are invariably spin-paired complexes except for vanadium metal.

4. The increase in bond length in CO as compared to carbon monoxide is due to :

(A) the donation of lone pair of electrons on the carbon into a vacant orbital of the m etal atom
(B) due to the donation of a pair of electrons from a filled d-orbital of metal into the vacant antibonding &* orbital
of carbon monoxide
m onoxide..
(C) (A) and (B) both
(D) none.

5. Which of the following statement is false for Nickel carbonyl [Ni(CO)4] ?

(A) It is a colourless compound.
(B) The Ni — C— O group is linear.
linear.
(C) The four carbonyl group are lyi
lying
ng at the corners of a regular tetrahedron
(D) The metal  – carbon bond length (for % bond) does not alter.

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6. Which amongst
am ongst the following metal carbonyls are inner orbital complexes
com plexes with diamagnetic property ?
(I ) Ni(CO)4; (II ) Fe(CO)5 ; (III ) V(CO)6 (IV) Cr(CO)6
Select the correct answer from the codes gives below :
(A) I and II only (B) II , III and IV only (C) II and IV only (D) I II and IV only
,

7. Which one of the following metal carbonyls involves the d2sp3 hybridisation for the formation of metal-carbon %
bonds and is paramagnetic ?
(A) [Cr(CO)6] (B) [ V(CO)6 ] (C) [ Mo(CO)6 ] (D) [W (CO)6 ]

8. Which of the following statement is correct for metal

m etal carbonyls?
(A) In general, the effective atomic number for a stable monomeric
monom eric carbonyl is equal to the atomic number of the
next inert gas except [V(CO)6].
(B) The metal -carbon bond in metal carbonyls possess both s and p character.
(C) The C-O bond length in [Cr(CO)6] is greater than that in [W(CO)6].
(D) All of these.

MATCH THE COLUMN

9. Match the pair of complexes given in column-I and the characteristic(s) given in column-II.
Column - I Column - II

(A) (NH4)2[NiCl4] and (NH4)2[Ni(CN)4] (p) Both show same electrical conductance.

(B) CoCl3.6NH3 and PtCl4.5NH3 (q) Both show

how sam
same
e eff
effec
ecttive
ive ato
atomi
mic
cnnum
umbe
berr.

(C) [Pt(NH3)2Cl2] and (NH4)2[PtCl4] (r) Both show same primary valencies.

(D) K2[Fe(H2O)6] and K4[FeCl6] (s) Both gives white participate with AgNO3 solution.

10. Match the complexes given in column-I with their characteristic(s) given in column- II.

Column  – I Column  – II

(A) [Ni(gly)2] (p) Square planar geometry

(B) [Ni(CO)4] (q) Tetrahedral geometry

(C) [NiCl(PPh3)3] (r) Oxidation state of nickel is + 2

(D) [Ni(dmg)2] (s) Chelating ligand

(t) Geometrical is
isomerism

11. Match the column.

Column - I Column - I I
(A) [Cr(H2O)5Br]2+ (p) Paramagnetic in nature

(B) [Cu(NH2CH2CH2NH2)Cl4]2  –
(q) Geom
Geome
etri
trical
cal isome
someri
rism
sm is exhi
exhibi
bitted

(C) [Pt(OX)2]2  –
(r) Optical is
isome
merrism is
is ex
exhibited
r
(D) [Fe(OH)4] (s) Do no
not fo
follow Sidewick E.
E.A.N. ru
rule

(t) Comp
Comple
lex
x hav
having
ing symme
symmetr
triical
cal bide
bident
ntat
ate
e ligan
igand
d

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ASSERTION / REASONING
DIRECTIONS :
Each question has 5 choices (A), (B), (C), (D) and (E) out of
o f which ONLY ONE is correct.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2
Statement-2 is NOT a correct explanation for
f or Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.
(E) Statement-1
Statement-1 and Statement-2 both are False.

12. Statement-1 : In the co-ordination complex [Pt(NH3)4 Cl2] Br2, a yellow precipitate of AgBr is obtained on
treating it with AgNO
AgNO3.
: Bromide ions are present as counter ions in the ionization sphere.
Statement-2 : Bromide

13. Statement-1 : In the complex [Co(NH3)3 Cl3], chloride ions satisfy the primary
primar y valencies as well as the secondary
valencies of cobalt metal.
: [Co(NH3)3Cl3] shows geometrical as well as optical isomerism.
Statement-2 : [Co(NH

14. Statement-1 : All the complexes of Pt (+II) and Au(+ III) with strong field as well as with weak field ligands are
square planar.
Statement-2 : The crystal field splitting "o is larger for second and third row transition elements , and for more
highly charged species. This larger value of "0 energetically favours the pairing of electron for square planar
geometry.

15. Statement-1 : The value of "o for M3+ complexes are always much higher than value for M2+ complexes (for the
same set of ligands)
Statement-2 : The crystal field stabilization energy of [Co(NH3)6]3+ < [Rh(NH3)6]3+

16. Statement-1 : The complex [Cr(SCN)(NH3)5 ]Cl

 ]Cl2 is linkage isomeric
isomer ic with [Cr(NCS)(NH3)5 ]Cl2.
 –
: SCN  is an ambident ligand in which there are two possible coordination sites.
Statement-2 : SCN

17. Statement-1 : The [Ni(en)3] Cl2 has higher stability than [Ni(NH3)6] Cl2
: In [Ni(en)3] Cl2, the geometry of Ni is octahedral.
Statement-2 : In

18. Statement-1 : Potassium ferrocyanide is diamagnetic where as potassium ferricyanide is paramagnetic.

: Crystal field splitting in ferrocyanide ion is greater than that of ferricyanide
Statement-2 : Crystal f erricyanide ion.

19. Statement-1 : In the reaction [CoCl2(NH3)4]+ + Cl  # 

 #$
 #$ [CoCl3(NH3)3] + NH3, when reactant is in cis-form two
 –

isomers of the product are obtained.

Statement-2 : Third
: Third chloride ion replaces an ammonia
amm onia cis to both chloride ion or trans to one of the chloride ion.

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20. Statement-1 : [NiF6]4 and [NiF6]2 both are high spin complexes.
 –  –

 –
: F  is a weak field ligand.
Statement-2 : F

21. St at em en t- 1 : The correct or der for the wave length of absorption in the visible region is ;
 –
[Ni(NO2)6]4  < [Ni(NH3)6]2+ < [Ni(H2O)6]2+
: The stability of different complexes depends on the strength of the ligand field of the various
Statement-2 : The
ligands.

22. Statement-1 : The cis-[CoCl2(en)2]+ has two enantiomers.

Statement-2 : 'en' is an bidentate mono anion.

TRUE / FALSE

23. [Ni(DMG)2] has geometry as that of the [Ni(PPh3)3Br].

24. The 'spin only' magnetic movement of an octahedral complex having CFSE = – 0.6 "0 and surrounded
surrounde d by weak
field ligands can be 4.9 BM or 1.73 BM

25. [Cr(C2O4)3]3  and [Cr(NH3)2Cl2(en)]+ both show cis-trans as well as optical isomerism.

 –

26. The IUPAC

IUPAC name of the complex K2[OsCl5N] is Potassium azidopentachloridoosmate(VI)
azidopentachloridoosmate(VI)

27. Sodium nitroprusside has iron in + II oxidation state and the complex is diamagnetic in nature.

28. The complex [Cu(NH3)4]2+ is tetrahedral with paramagnetic nature.

29. In iron pentacarbonyl, the oxidation state of iron is zero.

30. The correct formula of the coordination

coordination compound,
com pound, Bromidochloridobis(ethane-1,
Bromidochloridobis(ethane-1,2diamine)pl
2diamine)platinum(IV)
atinum(IV) nitrate
is [PtBrCl(en)2](NO3)2 .

31. Violet colour complex [Ti(H2O)6]3+ becomes colourless on heating.

32. The complex [Cr(H2O)6]Cl3 loses six water molecules to conc. H2SO4 and does not give any precipitate with
AgNO3.

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PART - I : MIXED OBJECTIVE

OBJECTIVE QUESTIONS (SINGLE CHOICE TYPE)

1. The IUPAC name of K2[Cr(CN) 2O2(O)2(NH3)] is :

(A) Potassiumamminedicyanodioxoperoxo chromate(VI)
(B) Potassiumamminecyanoperoxodioxo chromium(VI)
(C) Potassiuma mminecyanope roxodioxo chromium(VI)
(D) Potassiumamminecyanoperoxodioxo chromate(IV)

2. The correct name of [Pt(NH3)4Cl2] [PtCl4] is :

(A) Tetraamminedichloroplatinum(IV)
Tetraamminedichloroplatinum(IV) tetrachloroplatinate(II)
(B) Dichlorotetraammineplatinum
Dichlorotetraammineplatinum(IV)(IV) tetrachloro platinate(II)
(C) Tetrachloro
Tetrachloro platinum(II) tetraammine platinate(IV)
(D) Tetrachloro platinum(II) dichloro tetraamine platinate(IV)

3. The IUPAC name [Co(NH3)6] [Cr(CN)6] is :

(A) Hexaamminecobalt(III)hexacyano chromate(III)
(B) Hexacyanochromiumcobalt hexaammine(VI)
(C) Hexaammine cobalt(III)hexacyano chromium(VI)
(D) Hexacyanochromium(III
Hexacyanochromium(III)hexaammine
)hexaammine cobalt(III)

4. What is the oxidation number of chromium in the dimeric hydroxo bridged species ?
H 4+
O
(H2O)4 Cr Cr(H
Cr(H2O)4
O
H
(A) + 6 (B) + 4 (C) + 3 ( D) + 2

5. Which of the following name is impossible ?

(A) Potassi
Potassiumte
umtetra
traflu
fluorid
oridoox
ooxido
idochro
chromate
mate(VI
(VI)) (B) Bariu
Bariumte
mtetra
trafl
fluor
uorid
idobr
obroma
omate
te(II
(III)
I)
(C) Dichlorobis(urea)copper(II) (D) All are im
impossible.

1
6. Which of the following is most likely formula of platinum complex, if of total chlorine of the compound is
4
precipitated by adding AgNO3 to its aqueous solution ?
(A) PtCl4.6H2O (B) PtCl4.5H2O (C) PtCl4.2H2O (D) PtCl4.3H2O

7. 50 ml of 0.2 M solution
s olution of a compound with empirical formula CoCl3.4NH3 on treatment with excess
exc ess of AgNO3(aq)
yields 1.435 g of AgCl. Ammonia is not removed by treatment with concentrated H 2SO4. The formula of the
compound is :
(A) Co(NH3)4Cl3 (B) [Co(NH3)4Cl2]Cl (C) [Co(NH3)4Cl3 (D) [CoCl3(NH3)]NH3

8. If excess of AgNO3 solution is added to 100 mL of a 0.024 M solution of dichlorobis(ethylenediamine)cobalt

dichlorobis(ethylenediamine)cobalt (III)
chloride. How many moles of AgCl be precipitated ?
(A) 0.0012 (B) 0.0016 (C) 0.0024 (D) 0.0048

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9. How many moles of AgCl would be obtained, when 100 ml of 0.1 M Co(NH3)5Cl3 is treated with excess of
AgNO3?
(A) 0.01 (B) 0.02 (C) 0.03 (D) none of these

10. Which of the following is non –conducting ?

(A) CoCl3.6NH3 (B) CoCl3.5NH3 (C) CoCl3.4NH3 (D) CoCl3.3NH3

11. Consider the following statements :

S1 : [ MnCl6 ]3 , [ FeF6 ] 3 and [ CoF6]3 are paramagnetic having four , five and four unpaired electrons
 –  –  –

respectively.
S2 : Valence bond theory gives a quantitative interpretation of the thermodynamic stabilities of coordination
compounds.
S3 : The crystal field splitting "o , depends upon the field produced
pr oduced by the ligand and charge on the metal
m etal ion and
arrange in the order of true/ false.
(A) T T T (B) T F T (C) F T F (D) T F F

12. Which of the following complex is not correctly matched with its geometry ?
(A) [NiCl2(Ph3P)2]  – tetrahedral (B) [Co(Py)4]2+  – square planar.
(C) [Cu(CN)4]3  – tetrahedral
 –
(D) [Fe(CO)4]2  – square planar.
 –

13. Match Column-I with Column-II and select the correct answer with respect to hybridisation using the codes given
below :
Column - I Column - II
(Complex) (Hybridisation)
(I) [Au F4]  –
(p) dsp2 hybridisation
hybridisation
(II) [Cu(CN)4] 3  –
(q) 3
sp  hybridisation
(III) [Co(C2O4)3]3  –
(r) sp3d2 hybridisation
(IV) [Fe(H2O)5NO]2+ (s) d2sp3 hybridisation
Codes :
(I) (II) (III) (IV) (I) (II) (III) (IV)
(A) q p r s (B) p q s r
(C) p q r s (D) q p s r

14. All the metal ions contains t2g6 eg0 configurations. Which of the following complex will be paramagnetic?
(A) [FeCl(CN)4(O2)]4- (B) K4[Fe(CN)6] (C) [Co(NH3)6]Cl3 (D) [Fe(CN)5(O2)]-5

15. The complex [ Fe (H2O)5 NO+ ]2+ is formed in the ‘brown ring test’ for nitrates. Choose the incorrect statement
for the complex.
(A) Its magnetic moment is approximately 3.9 B.M.
(B) The oxidation state of iron is + 1
(C) The hybridisation of central metal ion is sp3 d2
(D) The brown colour of the ring is due to d  – d transition.

16. Which one of the following statement is false for nickel-dimethylgly

nickel-dim ethylglyoximate
oximate complex ?
(A) The stability of complex is only due to the presence of intra-molecular
intra-m olecular hydrogen bonding.
(B) The complex is stable because tridentate dimethyl glyoxime ligand forms a five membered chelate rings.
(C) The complex is stable as it has five membered chelate rings as well as intra molecular
m olecular hydrogen bonding.
(D) A and B both.

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17. Which of the following statements are correct for the complex [Co(NH3)4(Cl) (NO2)]Cl ?
1. Cobalt
Cobalt is in + 3 oxidatio
oxidation
n state involv ing d2sp3 hybridisation.
involving
2. Cobalt
Cobalt is in + 3 oxidation
oxidation state
state involvin g sp3d2 hybridisation.
involving
3. It shows
shows ionisation
ionisation as well
well as linkage
linkage isomerism.
isomerism.
4. It also
also shows
shows geometric
geometricalal isomerism.
isomerism.
(A) 1, 3 and 4 only (B) 2, 3 and 4 only (C) 1 and 4 only (D) 2 and 4 only.

18. Which of the following statements about Fe(CO)5 is correct?

(A) It is
is para
paramagn
magneti
etic
c and
and high
high spin
spin compl
complex
ex (B) It is
is diamag
diamagnet
netic
ic and
and high
high spin
spin comple
complex
x
(C)
(C) It
It is
is dia
diamag
magne
neti
tic
c and
and low
low spin
spin compl
complex
ex (D)
(D) It
It is para
paramag
magne
neti
tic
c and
and low
low spin
spin compl
complex
ex

19. Which of the following statements is not true?

0
(A) MnCl 4  ion has tetrahedral geometry and is paramagnetic.
(B) [Mn(CN)6]2  ion has octahedral geometry and is paramagnetic.
 –
param agnetic.
3  –
(C) [Cu(CN)4]  has square planar geometry and is diamagnetic.
(D) [Ni(Ph3P)2Br3] has trigonal bipyramidal geometry and is paramagnetic.

20. Arrange the following

following in order of decreasing number of unpaired electrons ?
! : [Fe(H2O)6]2+ !! : [Fe(CN)6]3
 –
!!! : [Fe(CN)6]4
 –
!V : [Fe(H2O)6]3+
(A) !V, !, !!, !!! (B) !, !!, !!!, !V (C) !!!, !!, !, !V (D) !!, !!!, !, !V

21. Which of the following complex does not show geometrical

geometrical isomerism ?
(A) [ Co (NH3)4 Cl2 ]+ (en)3 ]3+
(B) [ Co (NH3)3 (NO2)3 ] (C) [ Cr (e (D) [ Pt (gly)2]

22. [Fe(en)2(H2O)2]2+ + en $ complex(X). The correct statement about the complex (X) is :
(A) it is a low spin complex. (B) it is diamagnetic.
(C) it shows geometrical isomerism. (D) (A) and (B) both.

23. The complexes given below show :

 and

(A) optical isomerism (B) co-ordination isomerism

(C) geometrical isomerism (D) bridged isomerism

24. The total number of possible isomers of the compound [CuII(NH3)4] [PtIICl4] are:
(A) 3 (B) 5 (C) 4 (D) 6

25. On treatment of [Pt(NH3)4]2+ with concentrated HCl, two compounds (I) and (II) having the same formula,
[Pt(NH3)2Cl2] are obtained, (I) can be converted into (II) by boiling with dilute HCl. A solution
solution of (I)
( I) reacts with
oxalic acid to form [Pt(NH3)2(C2O4)] whereas (II) does not react. Point out the correct statement of the following.
(A) (I
(I) ci
cis, (I
(II) tr
trans; boboth te
tetrahedral (B) (I
(I) ci
cis, (I
(II) tr
trans; boboth square pl
planar
(C) (I
(I) tr
trans, (I(II) ci
cis; bo
both te
tetrahedral (D) (I
(I) tr
trans, (I(II) ci
cis; bo
both sq
square pl
planar

26. Which of the following complex will show optical activity ?

(A) trans-[Co(NH3)4Cl2]+ (B) [Cr(H2O)6]3+
(C) cis-[Co(NH3)2(en)2]3+ (D) trans-[Co(NH3)2(en)2]3+

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27. The complex ion has two optical isomers. Their correct configurations
conf igurations are :

(A) (B)

(C) (D)

28. Of the following complex ions, the one that probably has the largest overall formation constant, Kf, is :
(A) [Co(NH3)6]3+ (B) [Co(H2O)6]3+ (C) [Co(NH3)2(H2O)4]3+ (D) [Co(en)3]3+

29. What is the ratio of uncomplexed to complexed Zn2+ ion in a solution that is 10 M in NH3, if the stability constant
constant
of [Zn(NH3)4]  is 3 × 10  ?
2+ 9

(A) 3.3 × 10 9
 –
(B) 3.3 × 10 11  –
(C) 3.3 × 10 14  –
(D) 3 × 10 13  –

More than one choice type

30. In which of the following pairs of complexes the central metals/ions do have same effective atomic number ?
(A) [ Cr (CO)6 ] and [ Fe (CO)5 ] (B) [ Co (NH3)6 ]2+ and [Ni (NH3)6]2+
(C) [Cu (CN)4]3 and [ Ni (CO)4 ]
 –
(D) [V(CO)6]  and [Co(NO2)6]3
 –  –

31. Which of the following is/are correctly matched ?

(A) Ni(CO)4 _____ tetrahedral, paramagnetic (B) Ni(CN)4 ]2  _____ square planar, diamagnetic
 –

(C) Ni(dmg)2 _____ square planar, diamagnetic [NiCl4]2  _____ tetrahedral, paramagnetic

(D) [N  –

32. 'Spin only'

only' magnetic mom ent of Ni in [Ni(dmg)2] is same as that found in :
 –
(A) Ni in [NiCl 2 (PPh3)2] (B) Mn in [MnO4]
(C) Co in [CoBr4]2  –
(D) Pt in [Pt (H2O)2 Br2]

33. Which of the following statements is/are true for [Pt(NH3)(H2O)(Cl)2] ?

(A) It has diamagnetic character (B) It has square planar geometry
(C) It shows geometrical
geometrical and optica
opticall isomerism
isomerism (D) It shows only geometrical
geometrical isomerism
isomerism

34. Which of the following

f ollowing statement(s) is /are correct ?
(A) In K3[Fe(CN)6 ], the ligands has satisfied only the secondary valencies of ferric
ferr ic ion.
(B) In K3[Fe(CN)6], the ligands has satisfied both primary and secondary valencies of ferric
ferr ic ion.
(C) In K4[Fe(CN)6], the ligands has satisfied only the secondary valencies of ferrous ion.
(D) In [Cu(NH3)4]SO4, the ligands has satisfied only the secondary valencies of copper.

35. Which of the following statements is/are incorrect for the complex [Cr(H2O)6]Cl3 ?
(A) It has a magnetic moment of 3.83 BM.
(B) The distribution of 3d electrons is 3dxy1, 3dyz1, 3dzx1
(C) The ligand has satisfied both primary
prim ary and secondary valencies
valencies of chromium.
chromium .
(D) It shows ionization as well as hydrate isomerism.
isomerism .

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36. Which statements is/are correct ?

(A) [Ni(PPh3)2Br2] - tetrahedral and paramagnetic.
paramagnetic. (B) [Ni (CO)4] - tetrahedral and diamagnetic.
 –
2  –
(C) [Ni(CN)4]  - square
square plana
planarr and diama
diamagn
gneti
etic.
c. (D) [Ni(C l)4]2 square planar
[Ni(Cl) planar and diamagnetic.
diamagnetic.

 –  –
37. following statements is/are true for the complexes, [Fe(H2O)6]2+ , [Fe(CN)6]4  , [Fe(C2O4)3]3
Which of the following
and [Fe(CO)5] ?
(A) Only [Fe(C2O4)3]3  show optical isomerism.
 –

(B) [Fe(C2O4)3]3  is less stable than [Fe(CN)6]2

 –  –

(C) All complexes have same effective atomic number

num ber..
(D) [Fe(CO)5] shows back bonding.

38. [CoCl2(en)2]Br will show :

(A) coordinate position isomerism (B) ionization isomerism
(C) geometrical isomerism (D) optical isomerism.

39. In which of the following complexes more than one type of structural isomerism is possible ?
(A) [Co(NH3)5 (NO2)]Cl (B) [Co(NH3)5(H2O)](NO2)3
(C) [Pt(NH3)4][Pt(SCN)4] (D) [Cr(NH3)4 (NO2)2] (NO3)2

PART - II : SUBJECTIVE QUESTIONS

1. Name the follow

f ollowing
ing compounds(All these are important compounds, will be used in different fields of chemistry)
(c) [Fe(CO)5], A highly toxic volatile liquid.
(d)
(d) [Fe(C2O4)3]3 ,  –
The
The io
ion forme
med
d wh
when Fe
Fe2O3 rust is dissolved in oxalic acid, H2C2O4.
(e)
(e) [Cu(NH3)4]SO4, A deep
deep blue
blue compound
compound obtaine
obtained
d when
when CuSO4 is treated with excess of NH3.
(f)
(f) Na[Cr(OH)4], The
The comp
compou
ound
nd form
formed
ed when
hen Cr(O
Cr(OH)
H)3 precipitate is dissolved in excess of NaOH.
(g)
(g) Co(gly)3, A comp
compllex that
that con
contain
tains
s tth
he ani
anion
on of amino
mino aci
acid, gly
glycine
cine..
(h)
(h) analysis test of Fe3+ ion.
[Fe(H2O)5(SCN)]2+, The red complex ion form ed in the qualitative analysis
(i) K2[HgI4], Alkaline so
solution of
of th
this co
comp
mpllex is
is ca
called Nessler’s Reagent.
(j) Co[Hg(SCN)4], Deep blue
blue crystalli
crystalline
ne precipitat
precipitate
e obtained
obtained in qualitati
qualitative detection of Hg2+.
ve detection
(k) Fe4[Fe(CN)6]3, blue, deep blue colored complex obtained in detection of Fe2+.
Prussian blue,
(l) K3[Co(NO2)6], cobaltinitrite or Fischer salt yellow
Potassium cobaltinitrite or salt yellow precipitate obtained in detection of
2+
Co .
(m) [Ni(dmg)2], Rosy
Rosy red
red pre
preci
cipi
pita
tate
te obta
obtain
ined
ed in dete
detect
ctio
ion
n of Ni2+ ions.
of Ni
(n)
(n) K2[PtCl6], Yello
ellow
w pre
preci
cipi
pita
tate
te obta
obtain
ined
ed in det
detec
ecti
tion
on of pot
potas
assi
sium
um ion
ions(s
s(simi
imila
larr compl
complex
ex is for
formed
med
+
with NH4 ions also).
(o)
(o) Na2[Fe(CN)5NO+], Sodium nitroprusside used
nitroprusside used for detection of sulphide ions/sulphur.
ions/sulphur.
(p)
(p) [Fe(H2O)5(NO+)]SO4, Brown ring complex, obtained in detection of Fe2+ ions.

(q)
(q) [Cu(CN)4]3 ,  –
Colo
Colour
urle
less
ss sta
stabl
ble
e solu
solubl
ble
e compl
complex
ex obt
obtai
aine
ned
d in
in dete
detecti
ction of Cu2+ on adding excess of
on of
KCN solution.

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2. Write down the formulae

form ulae of the following compounds.
(a) diam
diammimine
netr
tria
iaqu
quah
ahy ydrox
droxididoc
ochrhrom
omiuiumm (II
(III)
I) nitr
nitrat
atee
(b)
(b) tetr
tetraki
akis(
s(py
pyri
ridi
dine
ne)p
)pla
lati
tinu
num(I
m(II)I) tetr
tetrap
aphehenynylb
lbor
orat
ate(
e(II
III)
I)
(c) dibromi
romiddotetracarb
carbo onyliron
ron (II
(II)
(d) minecobalt(III)-3-amido-3-hydroxidobis(ethylen
tetraammin -hydroxidobis(ethylenediamine)cobalt(III)
ediamine)cobalt(III) chloride
(e)
(e) ammon
ammoniu ium
m diamm
diammin inet
etet
etrak
rakisis(i
(isot
sothi
hioc
ocyayana
natoto)ch
)chro
romat
mate(
e(II
III).
I).
(f) pent
pentaa
aamm
mmin ined
edin
init
itro
roge
genrnrututhe
heni nium
um(I (II)
I) chlo
chloriride
de
(g) bis(cy
s(cyc
clopentadienyl)iro )ironn(II)
(h) bari
barium
um dihy
dihydr drox
oxid
idod
odininit
itri
rito
to-O
-O-o -oxa
xala
lato
tozi
zirc
rcon
onatate(
e(IV
IV))
(i)
(i) tetr
tetrap
apy
yridi
ridine
nepl plat
atin
inum
um(I (II)
I) tetr
tetrac
achlhlor
orid
idon
onicicke
kela
late
te(I
(II)
I)
(j) tetraammineaquacobalt(III)-3-cyanidotetraamminebromidocobalt(III)

3. (a) Arrange the following compounds in order

or der of increasing m olar conductivity.
conductivity.
(i) K[Co(NH3)2(NO2)4] (ii) [Cr(NH3)3(NO2)3] (iii) [Cr(NH3)5(NO2)]3[Co(NO2)6]2 (iv) [Cr(NH3)6]Cl3
(b) Deduce the value of x in the formulae of following
f ollowing complexes
(i) Mo(CO)x (ii) HxCr(CO)5 (iii) HxCo(CO)4

4. Complete the following table (using concepts of VBT).

Complex Geometry Hybridisation Number of unpaired electrons(n) Mag. moment
CN =2
(a) [Ag(NH3)2]+ - - - - - -- - - - - - - - - -- - - - - - - - - - - -- - - - - - - - - -- - - - - -
 0 ----------------------

 – - - - - - -- - - - - - - - - -- - - - - - - - - - - -- - - - - - - - - -- - - - - - - - - - - -- - - - - - - - - -- - - - - -
(b) [Cu(CN)2] Linear
 – - - - - - -- - - - - - - - - -- - - - - - - - - - - -- - - - - - - - - -- - - - - - - - - - - -- - - - - - - - - -- - - - - -
(c) [AuCl2]  0
CN = 4
- --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- - - --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- - ----------------------
(d) [PtCl2(NH3)2]  0
(e) [Zn(CN)4]2  – - --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- - - --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- -
 0 ----------------------

(f) [Cu(CN)4]3  – - --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- - - --
--- --
-- --
--- --
---- --
--- --
--- --
---
 0 ----------------------

(g) [MnBr4]2  – - --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- - - --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- -
 5 ----------------------

(h) [Cu(NH3)4]2+ Square Planar - - - - - -- - - - - - - - - -- - - - - - - - - - - -- - - - - - - - - -- - - - - - - - - - - -- - - - - - - - - -- - - - - -

(i) [CoI4]2 – - --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- - - --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- -
 3 ----------------------

CN = 6
(j) [Mn(CN)6]3  – - --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- - - --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- -
 2 ----------------------

(k) [Cr(NH3)6]3+ - - - - - -- - - - - - - - - -- - - - - - - - - - - -- - - - - - - - - -- - - - - -
 3 ----------------------

(l) [Fe(CN)6]3  – - --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- - - --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- -
 1 ----------------------

(m) [Ir(NH3)6]3+ - - - - - -- - - - - - - - - -- - - - - - - - - - - -- - - - - - - - - -- - - - - -
 0 ----------------------

- --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- - - --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- - ----------------------
(n) [V(CO)6]  1
(o) [Fe(H2O)6]2+ - - - - - -- - - - - - - - - -- - - - - - - - - - - -- - - - - - - - - -- - - - - -
 4 ----------------------

(p) [MnCl6]3  – - --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- - - --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- --
-- -
 4 ----------------------

5. (A), (B) and (C) are three complexes of chromium(III) with the empirical formula
form ula H12O6Cl3Cr. All the three complexes
com plexes
have water or chloride ion as ligands. Complex (A) does not react
reac t with concentrated H2SO4, whereas complexes
(B) and (C) lose 6.75% and 13.5% of their original weight, respectively,
respectively, on treatment with concentrated H2SO4.
(i) Identify (A), (B) and (C) (ii) W rite their formulae
(iii) Calculate their EAN. (iv) By the addition of AgNO3 what happens with each complex.

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6. A metal complex having composition Cr(NH3)4Cl2Br has been isolated in two forms A and B. The form A reacts
with AgNO3 to give a white precipitate
precipitate readily soluble in
in dilute aqueous ammonia, whereas B gives a yellow
precipitate soluble in concentrated ammonia.
(i)
(i) Write
Write the
the formu
formula
lae
e of A and
and B.B.
(ii)
(ii) State hybridis
hybridisation
ation of chromium
chromium in each.
(iii) Calculate their magnetic moments for each (spin-only value).
(iv) Calculate
Calculate the
the EAN
EAN for both.
both.
(v) Will they
they conduct
conduct electrici
electricity
ty or not.
not.
(vi)
(vi) Write the formula of the complexes formed when the precipitates dissolvedissolve in aqueous
aqueous ammonia & the
concentrated ammonia respectively.

7. (a) Which of the complexes (a) [Cr(edta)] , (b) [Ru(en)3]2+ and (c) [Pt(dien)Cl]+ are chiral ?
 –

(b) Give the IUPAC

IUPAC name of the complex, [IrH(CO)
[IrH( CO) (PMe3)2] and also give the hybridisation of the central atom
along with the magnetic moment.

8. Draw all the possible isomers of [Co (NH3)2 (en) Cl2 ]+.

9. (a) Draw all possible constitutional isomers of the compound Ru(NH3)5(NO2)Cl. Label the isomers as linkage
isomers or ionization isomers.
 –  –
(b) There are six possible isomers for a square planar palladium(II) complex
co mplex that contains two Cl  and two SCN
ligands. Sketch the structures of all six, and label them according to the c lassification.

10. Tell how many diastereoisomers are possible for each of the following
f ollowing complexes, and draw their structures.
2+
(a) [Cr(NH3)2Cl4]  –
(b) [Co(NH3)5Br] (c)[FeCl2(NCS)2]2  –

(d) [PtBr2Cl2]2
 –
(e) [Co(en)(SCN)
[Co(en)(SCN)4]  –
(f) [Cr(NH3)2(H2O)2Cl2]+ (g) [Ru(NH3)3I3]

11. Which of the following complexes can exist as enantiomers? Draw their structures.
(a) cis-[Co(NH3)4Br2]+ (b) cis-[Cr(H2O)2(en)2]3+ (c) [Cr(gly)3]
(d) [Cr(en)3]3+ (e) cis-[Co(NH3)Cl(en)2] 2+ trans-[Co(NH3)2(en)2]2+
(f) trans-[Co(NH

12. Predict the number of unpaired electrons in a tetrahedral d6 ion and in a square planar d7 ion.
Note : If answer in 1 and 2 represent as 12.

n4
13. From Meridional and facial isomer of [Ma 3b3 ]  on replacement of only one 'a' by 'b', the number of isomer of
the product obtained are ______ and _______ respectively
respec tively..
[If answer is 2 and 5 represent as 25]

14. In how many of the following entities the central metal ions have the oxidation state of + 2 ?
(a) [NiBr4]2  –
(b) [Fe(CN)6]3  –
(c) [MnBr4]2  –
(d) [AuCl4]  –

2+ 2+ 2  –
(e) [Fe(H2O)6] (f) [Pt(NH3)4] (g) [Co(SCN)4]

15. In Hx[Pt y6], y is monodentate negatively charged ligand then find out the value of x.

16. The total number of possible coordination isomer

isomer for the given compound is [Pt(NH3)4Cl2][PtCl4].

17. E.A.N. of K[PtCl 3( 1 2  –C2H4)] is :

18. The number of optically active isomer for [Pt(NH3)2(F)(Cl)(Br)(I)]° is ___________.

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19. How many of the following statements are incorrect ?

: cis - [M(NH3)2Cl2] would react with Ag2C2O4 but trans - isomer not.
(i) : cis
: Considering "0 to be same for Co(!!) and Co(!!!), the complex [Co(NH3)6]3+ is more stable than [Co(NH3)6]2+ .
(ii) : Considering
 –
: [V(CO)6] is more paramagnetic than [V(CO)6] .
(iii) : [V(CO)
: [Cr(gly)3] exists in two geometrical isomeric forms.
(iv) : [Cr(gly)
(v) [Co(NH3)3(NO3)3] has fac-and mer isomers.
(vi) [RhCl(PPh3)3] is diamagnatic with square
s quare planar geometry.

20. How many of the following cases, EAN rule will be followed ?
K4[Fe(CN)6] [Fe(NH3)6]3+ V(CO)6

[Pt(NH3)6]4+ [Ni(NH3)6]Cl2 [Fe(C5H5)2]

K[PtCl3(12  – C2H4) Mn2(CO)10 ZnCl42  –

21. Total number of stereoisomers of the complex with formula [Cr(gly)2(NH3)2]+

22. Total Number of stereoisomers of the complex with formula [Co(en)2(NH3)(H2O)]3+

23. Number of (n  –  1) d orbitals involved in the hybridisation of central metal ion in brown ring complex,
[Fe(H2O)5NO+]SO4 is :

24. How many of the following statements are correct for Nickel carbonyl [Ni(CO)4] ?
(i) It is a colourless compound.
(ii) The Ni — C— O group is linear.
linear.
(iii) The four carbonyl group are lying at the corners of a regular tetrahedron.
(iv) The metal  – carbon bond length (for % bond) does not alter.
alter.
(v) There is synergic interaction between nickel metal and ligand CO.
(vi) The oxidation state of nickel is zero.
(vii) The effective atomic number (EAN) of nickel atom is 34.

25. Number of pair of enantiomer of [Ma2b2cd] is :

26. In Na2[Fe(CN)5NOS], complex the number of unpaired electrons is :

27. How many of the following statements are correct ?

(i) Both
oth [Fe(CN))6]3+ and [Cu(en)2 (H2O)2]2+ are paramagnetic and both species contain one unpaired electron.
[Fe(CN
(ii)
(ii) Complex
Complex ion,
ion, [Mn(SCN))6]4  having t 32g e 2g  configuration is a high spin complex with ‘spin only’ magnetic
[Mn(SCN  –

moment close to 5.93 BM.

(iii)
(iii) Coordi
Coordinat
nation
ion compound
compounds,s, CoCl3 . 6NH3 and PtCl4 . 5NH3 have the same magnetic properties and approximately
the same electric conductance for their 0.001 M aqueous solutions.
(iv) The compl
complexex [W(CO)
[W(CO)4(py)2] can exist in cis-and trans-isomers and its cis-form is optically inactive.
 –
(v) [Cu(CN
u(CN))4]  is parama
paramagnetic
gnetic with tetrahedral geometry.
geome try.
(vi) [Ti(
[Ti(H
H2O)6]Cl3 develops violet colouration in aqueous solution.

28. How many complexes among the following

following are paramagnetic ?
[Mn(CN)6]3 ,  –
[Cr(H2O)6]3+, [Co(en)3]3+,
[V(CO)6], [Ni(NH3)6]2+, [Ni(dmg)2],
[Pt(Cl)2(NH3)2], [Cu(NH3)4]2+, [Cu(CN)4]3 . –

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 COORDINATION COMPOUNDS

PART - I : IIT-JEE PROBLEMS (PREVIOUS YEARS)

* Marked Questions are having more than one correct option.

1. Draw the structures of [Co(NH3)6]3+, [Ni(CN)4]2  and [Ni(CO)4]. Write the hybridisation of atomic orbitals of the
 –

transition metal in each case. [JEE –2000, 3/100]

2. The complex ion which

which has no 'd' electrons in the central metal atom is : [JEE –2001, 1/35]
[Atomic number Cr = 24, Mn = 25, Fe = 26, Co = 27]
(A) [MnO4 ¯ 
 ]¯  (B) [Co(NH3)6]3+ (C) [Fe(CN)6]3 (D) [Cr(H2O)6]3+
 –

3. A metal complex having composition Cr(NH3)4 Cl2Br has been isolated in two forms A and B. The form A reacts
with AgNO3 to give a white precipitate readily soluble in dilute aqueous ammonia,
ammo nia, where as B gives a pale yellow
precipitate soluble in concentrated ammonia. Write
W rite the formula
form ula of A and B and state the hybridization of chromium
in each. Calculate their magnetic moments (spin only value). [JEE –2001, 5/100]

4. Deduce the structure of [NiCl4]2  and [Ni(CN)4]2  considering the hybridisation of the metal
 –  –
m etal ion. Calculate the
magnetic moment (spin only) of the species. [JEE –2002, 5/60]

5. A green complex, K2[Cr(NO)(NH3)(CN)4] is paramagnetic and has 3eff = 1.73 BM. Write
W rite the IUPAC
IUPAC name of the
complex and draw the structure of anion and find out the hybridisation of metal ion. [JEE –2003, 4/60]

6. The species having tetrahedral shape is : [JEE –2004, 3/84]

(A) [PdCl4]2 –
(B) [Ni(CN)4]2  – 2 –
(C) [Pd(CN)4] (D) [NiCl4] 2 –

7. The spin magnetic moment of cobalt in the compound, Hg [Co(SCN)4] is : [JEE –2004, 3/84]
(A) 3 (B) 8 (C) 15 (D) 24

8. When dimethyl glyoxime is added to the aqueous solution of nickel (II) chloride in presence of dilute ammonia
solution, a bright red coloured precipitate is obtained. [JEE –2004, 4/60]
(a) Draw the structure of bright red substance.
s ubstance.
(b) Write the oxidation state of nickel in the substance and hybridisation.
(c) State whether the substance is paramagnetic or diamagnetic.

9. Which kind of isomerism is exhibited by octahe

octahedral
dral [Co(NH3)4Br2]Cl ? [JEE –2005, 3/84]
(A) Geometrical and ionization (B) Geometrical and optical
(C) Optical and ionization (D) Geometrical only

10. In the given reaction sequence, Identify (A) and (B).

0 0
Fe3+ +  # SCN
 #  # 
 # $ A F ( excess)
 #  #  #  #  # $  colourless(B)
Blood red
(Excess )

(a) Wri
Write th
the IU
IUPAC na
name of (A
(A) an
and (B
(B).
(b) Fin
Find out
out the
the sp
spin only
only ma
magn
gnet
etiic mom
momenentt of
of B.
B. [JEE –2005, 4/60]

11. The bond length in CO is 1.128 Å. What will

will be the bond length of CO in Fe(CO)5 ? [JEE –2006, 5/184]
(A) 1.158 Å (B) 1.128 Å (C) 1.178 Å (D) 1.118 Å

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 COORDINATION COMPOUNDS
Comprehension # (Q.12 to Q.14)
KCN
NiCl2  #  #
 # $ complex A
HCN

KCl
NiCl2  #  #
 # $ complex B
excess
A & B complexes have the co-ordination number 4.

12. IUPAC name of com plexes  A

The IUPAC ‘ ’ & ‘B’ are respectively : [JEE –2006, 5/184]
(A) Potassium tetracyanonickelate(!!) and Potassium tetrachloronickelate(!!)
(B) Potassium tetracyanonickel(!!) and Potassium tetrachloronickel(!!)
(C) Potassium cyanonickelate(!!) and Potassium chloronickelate(!!)
(D) Potassium cyanonickel(!!) and Potassium chloronickel(!!)

13. The hybridisation of both complexes are : [JEE –2006, 5/184]

(A) dsp2 (B) sp2 & dsp2 2
(C) dsp  & sp 3
(D) both sp 3

14. What are the magnetic nature of  A ‘ ’ & ‘B’ ? [JEE –2006, 5/184]
(A) Both diamagnetic.
(B)  A
‘ ’ is diamagnetic & ‘B’ is paramagnetic with one unpaired electrons.

(C)  A
‘ ’ is diamagnetic & ‘B’ is paramagnetic with two unpaired electrons.

(D) Both are paramagnetic.

15. Among the following metal carbonyls, the C  – O bond order is lowest in : [JEE –2007, 3/162]
(A) [Mn(CO)6]+ (B) [V(CO)6 ¯ 
 ]¯  (C) [Cr(CO)6)] (D) [Fe(CO)5]

16. Match the complexes in Column-I with their properties listed in Column-II. [JEE –2007, 6/162]
Column-I Column-II
(A) [Co(NH3)4(H2O)2]Cl2 (p) Geometrical is
isomers
(B) [Pt(NH3)2Cl2] (q) Paramagnetic
(C) [Co(H2O)5Cl]Cl (r) Diamagnetic
(D) [Ni(H2O)6]Cl2 (s) Metal ion wi
with +2
+2 ox
oxidation st
state

17. The IUPAC

IUPAC name of [Ni(NH3)4] [NiCl4] is : [JEE –2008, 3/163]
(A) Tetra
Tetrachl
chloro
oronic
nickel(
kel(II)
II) tetraa
tetraammin
mmineni
enickel
ckel (II)
(II) (B) Tetra
Tetraammi
amminen
nenicke
ickel(I
l(II)
I) tetrach
tetrachlor
loroni
onickel
ckel (II)
(II)
(C) Tetraammine
Tetraamminenickel
nickel(II)
(II) tetrachloronickel
tetrachloronickelate
ate (II) (D) Tetraammineni
Tetraamminenickel(II
ckel(II)) tetrachloroni
tetrachloronickelate
ckelate (0)

18. Both [Ni(CO)4] and [Ni(CN)4]2  are diamagnetic. The hybridisation of nickel in these complexes, respectively
 –
r espectively,, are :
  [JEE –2008, 3/163]
3 3 3 2 2 3
(A) sp , sp (B) sp , dsp (C) dsp , sp (D) dsp , sp2
2

19. Statement - 1 : The geometrical isomers of the complex [M(NH3)4Cl2] are optically inactive, and
Statement - 2 : Both geometrical isomers of the complex [M(NH3)4Cl2] possess axis of symmetry.
  [JEE –2008, 3/163]
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
Statement-1.
(B) Statement-1 is True, Statement-2
Statement-2 is True; Statement-2
Statement-2 is NOT a correct explanation for Statement-1
Statement-1
(C) Statement-1 is True, Statement-2 is False
(D) Statement-1 is False, Statement-2
Statement-2 is True

20. Statement - 1 : [Fe(H2O)5NO]SO4 is paramagnetic, and

Statement - 2 : The Fe in [Fe(H2O)5NO]SO4 has three unpaired electrons.   [JEE –2008, 3/163]
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
Statement-1.
(B) Statement-1 is True, Statement-2
Statement-2 is True; Statement-2
Statement-2 is NOT a correct explanation for Statement-1
Statement-1
(C) Statement-1 is True, Statement-2 is False
(D) Statement-1 is False, Statement-2
Statement-2 is True

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 COORDINATION COMPOUNDS

21. The compound(s) that exhibit(s) geometrical isomerism is(are) : [JEE –2009, 4/160]
(A) [Pt(en)Cl2] (B) [Pt(en)2]Cl2 (C) [Pt(en)2Cl2]Cl2 (D) [Pt(NH3)2Cl2]

22. The spin only magnetic moment value (in Bohr magneton units) of Cr(CO)6 is : [JEE –2009, 3/160]
(A) 0 (B) 2.84 (C) 4.90 (D) 5.92

23. The correct structure of ethylenediaminetetraacetic acid (EDTA) is : [JEE –2010, 3/163]

(A)

(B)

(C)

(D)

24. The ionization isomer of [Cr(H2O)4Cl (NO2)]Cl is : [JEE –2010, 3/163]

(A) [Cr(H2O)4(O2N)]Cl2 (B) [Cr(H2O)4Cl2](NO2)
(C) [Cr(H2O)4Cl(ONO)]Cl (D) [Cr(H2O)4Cl2(NO2)].H2O

25. The complex showing a spin-only magnetic moment of 2.82 B.M. is : [JEE –2010, 5/163]
(A) Ni(CO)4 (B) [NiCl4]2  –
(C) Ni(PPh3)4 (D) [Ni(CN)4] 2 –

26. Total number of geometrical isomers for the complex [RhCl(CO)(PPh3)(NH3)] is : [JEE –2010, 3/163]

27. Geometrical shapes of the complexes formed form ed by the reaction Ni2+ with Cl , CN  and H2O, respectively, are :
 –  –

[JEE –2011,3/240]
2011, 3/240]
(A) octa
octahe
hedra
dral,
l, tetr
tetrah
ahedr
edral
al and
and squar
square
e plana
planarr (B) tetr
tetrahe
ahedra
dral,
l, squa
square
re plana
planarr and octa
octahe
hedra
drall
(C) squ
square
are pla
planar
nar,, tetrah
tetrahedr
edralal and
and octahe
octahedra
drall (D) octa
octahed
hedral
ral squa
square
re plana
planarr and octa
octahed
hedral
ral

28. Among the following complexes (K-P)

K3[Fe(CN)6] (K),
(K), [Co(NH3)6]Cl3 (L),
(L), Na3[Co(oxalate)3] (M),
(M), [Ni(H2O)6]Cl2(N),
(N),
K2[Pt(CN)4] (O) and
(O) and [Zn (H2O)6] (NO3)2 (P)
the diamagnetic complexes are : [JEE –2011,3/240]
2011, 3/240]
(A) K, L, M, N (B) K, M, O, P (C) L, M, O, P (D) L, M, N, O

29. The colour of light absorbed by an aqueous solution of CuSO4 is : [JEE –2012, 3/210]
(A) orange-red (B) blue-green (C) yellow (D) violet

30. As per IUPAC

IUPAC nomenclature, the name of the com plex [Co(H2O)4 (NH3)2]Cl2 is : [JEE-2012, 3/210]
(A)
(A) Tetra
etraaq
aqua
uadi
diam
amin
inec
ecob
obal
altt (III
(III)) chlo
chlori
ride
de (B)
(B) Tetra
etraaq
aqua
uadi
diam
ammi
mine
neco
coba
balt
lt (III
(III)) chlo
chlori
ride
de
(C)
(C) Diam
Diamininet
ete
etraa
traaqu
quaacob
cobalt
alt (III
(III)) chl
chlori
oride (D)
(D) Diam
Diammimine
nete
tetr
traa
aaqu
qua
acoba
coballt (III
(III)) chl
chlori
oride

31. NiCl2{P(C2H5)2(C6H5)}2 exhibits temperature dependent magnetic behaviour (paramagnetic/diamagnetic). The

coordination geometries of Ni2+ in the paramagnetic and diamagnetic states are respectively
respect ively[JEE-2012,
[JEE-2012, 3/198]
(A) tetrahedral and tetrahedral (B) square planar and square planar
(C) tetrahedral and square planar (D) square planar and tetrahedral

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 COORDINATION COMPOUNDS

PART - II : AIEEE
AIEEE PROBLEMS (PREVIOUS YEARS)

1. A square planar complex is formed by hybridization of which atomic orbitals ? [AIEEE – 2002]

(1) s, px, py, dyz (2) s, px, py, dx2  y2 (3) s, px, py, dz2
 –
(4) s, px, py, dx y

2. The type of isomerism present in nitropentaamminechromium(III) chloride is : [AIEEE – 2002]

(1) optical (2) linkage (3) ionization (4) polymerization

3. In the complex [Fe(H2O)6]3+  [Fe(CN)6]3 , [Fe(C2O4)3]3  and [FeCl6]3  , more stability is shown by :
 –  –  –

[AIEEE – 2002]
3+ 3  – 3  – 3  –
(1) [Fe(H2O)6] (2) [Fe(CN)6] (3) [Fe(C2O4)3] (4) [FeCl6]

4. One mole of Co(NH3)5Cl3 gives 3 moles of ions on dissolution

diss olution in water. One mole of this reacts with two moles of
AgNO3 to give two moles of AgCl. The complex is : [AIEEE – 2003]
(1) [Co(NH3)4Cl2]Cl.NH3 (2) [Co(NH3)4Cl]Cl2.NH3 (3) [Co(NH3)5Cl]Cl2 (4) [Co(NH3)3Cl3].2NH3

5. Ammonia forms the complex [Cu(NH3)4]2+ with copper ions in alkaline solution but not in acid solution. The
reason for it is : [AIEEE – 2003]
(1) in alkaline solution Cu(OH)2 is precipitated which is soluble in excess of alkali.
(2) copper hydroxide is amphoteric.
(3) in acidic solution hydration protects Cu2+ ions.
(4) in acidic solution protons coordinates with ammonia molecule form ing NH4+ ions and NH3 molecules are not
available.

6. In the coordination compound K4[Ni(CN)4], the oxidation state of nickel is : [AIEEE – 2004]

(1)  – 1 (2) 0 (3) + 1 (4) + 2

7. The co-ordination number of a central metal atom in a complex is determined by : [AIEEE – 2004]

(1) the number of only anionic ligands bonded
bonded to metal ion
(2) the number of ligands around a metal ion bonded by pi bonds
(3) the number of ligands around a metal
m etal ion bonded by sigma and pi bonds
(4) the number of ligands around a metal ion bonded by sigma bonds

8. Which one is an outer orbital complex ? [AIEEE – 2004]

(1) [Ni(NH3)6]2+ (2) [Mn(CN)6]4  –
(3) [Co(NH3)6] 3+
(4) [Fe(CN)6] 4 –

9. Co-ordination compounds have great importance in biological systems. In this context, which statement is
incorrect ? [AIEEE – 2004]
(1) Carboxypeptidase – A is an enzyme
enzyme and contains zinc.
zinc.
(2) Haemoglobin is the red pigment of blood and contains iron.
(3) Cyanocobalmin is B12 and contains cobalt.
(4) Chlorophylls are green pigments in plants and contain calcium.

10. Which one has largest number of isomers ? [AIEEE – 2004]

(1) [Co(en)2Cl2]+ (2) [Co(NH3)5Cl]2+ (3) [Ir(PhR3)2H(CO)] 2+
(4) [Ru(NH3)4Cl2] +

11. The correct order of magnetic moments (only spin value in BM) among is : [AIEEE – 2004]
(1) Fe(CN)64  > [CoCl4]2  > [MnCl4]2
 –  –  –
(2) [MnCl4]2  > [Fe(CN)6]4  > [CoCl4]2
 –  –  –

4 2 2
 –  –
(3) [Fe(CN)6]  > [MnCl4]  > [CoCl4]  –
(4) [MnCl4]2  > [CoCl4]2  > [Fe(CN)6]4
 –  –  –

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 COORDINATION COMPOUNDS

12. The oxidation state of Cr in [Cr(NH3)4Cl2]+ is : [AIEEE – 2005]

(1) 0 (2) +1 (3) +2 (4) +3

13. The IUPAC name of K3Fe(CN)6 is : [AIEEE – 2005]

(1) Potassium hexacyanoferrate(II) (2) Potassium hexacyanoferrate(III)
(3) Potassium hexacyanoiron(II) (4) Tripotassium hexacyanoiron(II)

14. Which of the following

f ollowing will
will show optical isomerism ? [AIEEE – 2005]
(1) [Cu(NH3)4]2+ (2) [ZnCl4]2  –
(3) [Cr(C2O4)3]3  –
(4) [Co(CN)6]3  –

15. The value of 'spin only' magnetic moment for

f or one of the following configurations is 2.84 BM. The correct one is:
(1) d4 (i
 (in strong field ligand) (2) d4 (in weak field ligand) [AIEEE – 2005]
(3) d3 (in
 (in weak
eak as
as wel
welll as stro
stron
ng fie
field
ld ligan
igand)
d) (4) d5 (in strong field
(4) f ield ligand)

16. Which one of the following complexes would exhibit

exhibit the lowest value of paramagnetic behaviour ?
[AIEEE – 2005]
(1) [Co(CN)6]3  –
(2) [Fe(CN)6]3  –
(3) [Mn(CN)6]3  –
(4) [Cr(CN)6]3  –

17. com bines with a uninegative monodentate ligand X to form a paramagnetic complex [NiX4]2 The
Nickel (Z = 28) combines  –  –

number of unpaired electron(s) in the nickel and geometry of this complex ion are, respectively :
(1) one, tetrahedral (2) two, tetrahedral [AIEEE – 2006]
(3) one, square planar (4) two, square planar

18. The IUPAC

IUPAC name for the complex [Co(NO2) (NH3)5]Cl2 is : [AIEEE – 2006]
(1) Nitr
Nitrit
ito-
o-N-
N-pe
pent
ntaa
aammi
mmine
neco
coba
balt
lt(I
(III
II)) chlo
chlori
ride
de (2) Nitri
Nitrito
to-N
-N-pe
-pent
ntaa
aammi
mmine
neco
coba
balt
lt(I
(II)
I) chlori
chloride
de
(3) Pen
Penta
taamm
ammin
inen
enit
itri
rito
to-N-
-N-co
coba
balt
lt(I
(II)
I) chlo
chlori
ride
de (4) Pen
Penta
taamm
ammin
inen
enit
itri
rito
to-N-
-N-co
coba
balt
lt(I
(III
II)) chlor
chlorid
ide
e

19. In Fe(CO)5, the Fe  – C bond possesses : [AIEEE – 2006]

(1) &-character only (2) both % and & characters
(3) ionic character only (4) %-character only

20. How many EDTA

EDTA (ethylenediaminetetr
(ethylenediaminetetraacetic
aacetic acid) molecules are required
r equired to make an octahedral
octahe dral complex with
a Ca2+ ion ? [AIEEE – 2006]
(1) Six (2) Three (3) One (4) Two

21. The 'spin only' magnetic moment (in units of Bohr magneton, 3B) of Ni2+ in aqueous solution would be
(atomic number Ni = 28) [AIEEE – 2006]
(1) 2.84 (2) 4.80 (3) 0 (4) 1.73

22. Which one of the following

f ollowing has a square planar geometry? [AIEEE 2007, 2/120]
(1) [NiCl4]2
 –
(2) [PtCl4]2 –
(3) [CoCl4]2 –
(4) [FeCl4]2
 –

(At. no. Co = 27, Ni = 28, Fe = 26, Pt = 78)

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 COORDINATION COMPOUNDS

23. The coordination number

numb er and the oxidation state of the element 'E' in the complex [E(en)2(C2O4)] NO2 (when 'en'
is ethylene diamine) are, respectively,
respectively, [AIEEE 2008, 3/105]
(1) 4 and 2 (2) 4 and 3 (3) 6 and 3 (4) 6 and 2

24. In which of the following octahedral complexes of Co (at no. 27), will the magnitude of "0 be the highest?
[AIEEE 2008, 3/105]
(1) [Co(C2O4)3]3  –
(2) [Co(H2O)6]3+ (3) [Co(NH3)6]3+ (4) [Co(CN)6]3  –

25. Which of the following has an optical isomer ? [AIEEE 2009, 4/144]
(1) [Co(en) (NH3)2]2+
[Co (en)(NH (2) [Co(H2O)4 (en)]3+ [Co (en)2 (NH3)2]3+
(3) [Co(en) [Co (NH3) 3 Cl]+
(4) [Co(NH

26. Which of the following

f ollowing pairs represents linkage isomers ? [AIEEE 2009, 4/144]
(1) [Pd(PPh3)2 (NCS)2] and [Pd(PPh3)2 (SCN)2] (2) [Co(NH3)5 NO
 NO3] SO4 and [Co (NH3)5 (SO4)] NO3
(3) [PtCl2 (NH3)4 Br
 Br2 and [Pt Br2 (NH3)4] Cl2 (4) [Cu (NH3)4] [Pt Cl4] and [Pt (NH3)4 [CuCl4]

27. A solution containing 2.675 g of CoCl3 . 6 NH3  (molar mass = 267.5 g mol 1) is passed through a cation
 –

exchanger. The chloride ions obtained in solution were treated with excess of AgNO3 to give 4.78 g of AgCl
(molar mass = 143.5 g mol 1). The formula of the complex
 –
com plex is (At. mass of Ag = 108 u) [AIEEE 2010, 8/144]
(1) [Co(NH3)6 ] Cl3 (2) [CoCl2 (NH3)4] Cl (3) [CoCl3(NH3)3] (4) [CoCl(NH3)5] Cl2

28. Which one of the following has an optical isomer ? [AIEEE 2010, 4/144]
(1) [Zn(en)(NH3)2]2+ (2) [Co(en)3]3+ (3) [Co(H2O)4(en)]3+ (4) [Zn(en)2]2+
(en = ethylenediamine)

29. Which of the following

f ollowing facts about the complex [Cr(NH3)6] Cl3 is wrong ? [AIEEE 2011, 4/144]
(1) The complex involves d2 sp3 hybridisation and is octahedral is shape
(2) The complex is paramagnetic
(3) The complex is an outer orbital complex
(4) The complex
com plex gives white precipitate with silver nitrate solution

30. mom ent (spin only) of [NiCl4]2 is :

The magnetic moment  –
[AIEEE 2011, 4/144]
(1) 1.82 BM (2) 5.46 BM (3) 2.82 BM (4) 1.41 BM

31. Which among the following will be named as dibromidobis(ethylen

dibromidobis(ethylene
e diamine) chromium(III) bromide ?
[AIEEE 2012, 4/120]
 –
(1) [Cr(en)3 Br3 (2) [Cr(en)2 Br2] Br (3) [Cr (en)Br4] (4) [Cr (en) Br2] Br

32. Which of the following complex species is not expected to exhibit optical isomerism ? [AIEEE 2013]

(1) [Co(en)3]3+ (2) [Co(en)2Cl2]+ (3) [Co(NH3)3Cl3] (4) [Co(en)(NH3)2Cl2]+

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 COORDINATION COMPOUNDS

NCERT QUESTIONS

1. coordination compounds in terms of W erner’s postulates.

Explain the bonding in coordination

2. FeSO4 solution mixed with (NH4)2SO4 solution 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?

3. Explain with two examples each of the following: coordination entity,

entity, ligand, coordination number, coordination
polyhedron,
polyhedron, homoleptic and heteroleptic.

4. What is meant by unidentate, didentate and ambidentate ligands? Give two examples for each.

5. Specify the oxidation

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]

6. Using IUPAC
IUPAC norms write the formulas
form ulas for the following
f ollowing :
(i) Tetrahydroxozincate(II) (ii) Potassium te
tetrachloridopalladate(II)
(iii) Diammin
minedichloridoplatinum(II) (iv) Potassi
ssium tetracyanonickelate(II)
(v) Pentaamminminenitrito-O-cobalt(III) (vi) Hexaamminminecobalt(III) sulphate
(vi
(vii) Pot
Potassiu
sium tri
tri(oxalato)ch
)chroma
matte(III) (vi
(viii) Hex
Hexaamm
mmiineplatinum(I
m(IV)
(ix) Tetrabromidocuprate(II) (x) Pentaamminenitrito-N-cobalt(III)

7. Using IUPAC
IUPAC norms write the systematic names of the following:
f ollowing:
(i) [Co(NH3)6]Cl3 (ii) [Pt(NH3)2Cl(NH2CH3)]Cl
(iii) [Ti(H2O)6]3+ (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]

8. List various types of isomerism possible for coordination compounds, giving an example of each.

9. How many geometrical isomers are possible in the following

f ollowing coordination entities?
(i) [Cr(C2O4)3]3
 –
(ii) [Co(NH3)3Cl3]

10. Draw the structures of optical isomers of :

(i) [Cr(C2O4)3]3
 –
(ii) [PtCl2(en)2]2+ (iii) [Cr(NH3)2Cl2(en)]+

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)]+

12. Write all the geometrical isomers of [Pt(NH3)(Br)(Cl)(py)] and how many of these will exhibit optical isomers?

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.

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 COORDINATION COMPOUNDS

14. What
Wha t 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?

15. Discuss 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  –

16. Draw figure to show the splitting of d orbitals in an octahedral crystal field.

17. What is spectrochemical series? Explain the difference between a weak field ligand and a strong field
f ield ligand.

18. splitting energy? How does the magnitude of "0 decide the actual configuration of d orbitals
What is crystal field splitting
in a coordination entity?

19. [Cr(NH3)6]3+ is paramagnetic while [Ni(CN)4]2  is diamagnetic. Explain why?

 –

20. A solution of [Ni(H 2O)6]2+ is green but a solution of [Ni(CN)4]2  is colourless. Explain.
 –

21. [Fe(CN)6]4 and [Fe(H2O)6]2+ are of different colours in dilute solutions. Why?

 –

22. Discuss the nature of bonding in metal carbonyls.

23. Give the oxidation state, d orbital occupation and coordination number
num ber of the central m etal ion in the following
complexes:
(i) K3[Co(C2O4)3] (iii) (NH4)2[CoF4] (ii) cis-[Cr(en)2Cl2]Cl (iv) [Mn(H2O)6]SO4

24. Write down the IUPAC

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-]Cl 2
(iii) CrCl3(py)3 (iv) Cs[FeCl4] (v) K4[Mn(CN)6]

25. What is meant by stability of a coordination compound in solution? State the factors which govern stability of
complexes.

26. What is meant by the chelate effect? Give an example.

27. Discuss briefly giving an example in each case the role of coordination compounds in :
(i) bibiological sysystems (ii) medicinal chemistry and
(iii
(iii)) ana
anallytica
ticall che
chemi
mist
stry
ry (iv
(iv) ext
extract
ractiion/m
on/me
etall
tallur
urg
gy of me
meta
tals
ls..

28. How many ions are produced from the complex Co(NH3)6Cl2 in solution?
(i) 6 (ii) 4 (iii) 3 (iv) 2

29. Amongst the following ions which one has the highest magnetic mom ent value?
(i) [Cr(H2O)6]3+ (ii) [Fe(H2O)6]2+ (iii) [Zn(H2O)6]2+

30. The oxidation number of cobalt in K[Co(CO)4] is :

(i) + 1 (ii) + 3 (iii)  – 1 (iv)  – 3

31. Amongst the following, the most stable complex is :

(i) [Fe(H2O)6]3+ (ii) [Fe(NH3)6]3+ (iii) [Fe(C2O4)3]3 (iv) [FeCl6]3
 –  –

32. What will be the correct order for the wavelengths of absorption in the visible region for the following :
[Ni(NO2)6]4 ,
 –
[Ni(NH3)6]2+, [Ni(H2O)6]2+ ?

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 COORDINATION COMPOUNDS

EXERCISE # 1
PART # I
A-1. (A) A-2. (B) A-3. (D)
(D) A-4. (D)
(D) A-5. (A) A-6. (D)
(D) A-7. (B)
A-8. (A) A-9. (C)
(C) B-1. (C)
(C) B-2. (C)
(C) B-3. (A) B-4. (B) B-5. (D)
(D)
B-6. (C)
(C) B-7. (B) B-8. (B) B-9. (C)
(C) B-10. (B) B-11. (A) B-12. (C)
(C)
B-13. (D)
(D) B-14. (C)
(C) C-1. (A) C-2. (C)
(C) C-3. (A) C-4. (A) C-5. (C)
(C)
C-6. (B) C-7. (C)
(C) C-8. (A) C-9. (B) C-10. (B) C-11. (B) C-12. (C)
(C)
C-13. (D)
(D) C-14. (C)
(C) D-1. (D)
(D) D-2. (A) D-3. (A) E-1. (D)
(D) E-2. (C)
(C)
E-3. (A) E-4. (A) E-5. (A) E-6. (C)
(C) E-7. (D)
(D) E-8. (C)
(C) E-9. (C)
(C)
E-10. (C)
(C) E-11. (C)
(C) F-1. (C)
(C) F-2. (B) F-3. (D)
(D) G-1. (A) G-2. (C)
(C)
G-3. (A) G-4. (C)
(C) G-5. (A) G-6. (C)
(C) G-7. (D)
(D) G-8. (C)
(C) G-9. (B)
G-10. (D)
(D) G-11. (D)
(D) G-12. (C)
(C) G-13. (C)
(C) G-14. (C)
(C) H-1. (C)
(C) H-2. (B)
H-3. (B) H-4. (C)
(C) H-5. (C)
(C) I-1. (D)
(D) I-2. (D)
(D) I-3. (C)
(C) I-4. (A)
I-5. (D)
(D) I-6. (C)
(C) I-7. (D)
(D)
PART # II
1. (B) 2. (D)
(D) 3. (A) 4. (B) 5. (D)
(D) 6. (C)
(C) 7. (B)
8. (D)
(D) 9. (A  – p, q, r) ; (B  – p, s); (C  – q, r) ; (D  – q, r)
10. (A  – p, r, s, t) ; (B  – q) ; (C  – q) ; (D  – p, r, s) 11. (A – p,s) ; (B  – p, s, t) ; (C  – s, t) ; (D  – p, s)
12. (A) 13. (C)
(C) 14. (A) 15. (B) 16. (A) 17. (B) 18. (C)
(C)
19. (A) 20. (D)
(D) 21. (B) 22. (C)
(C) 23. False 24. True 25. False
26. False 27. True 28. False 29. True 30. True 31. True 32. False

EXERCISE # 2 
PART # I
1. (A) 2. (A) 3. (A) 4. (C)
(C) 5. (A) 6. (D)
(D) 7. (B)
8. (C)
(C) 9. (B) 10. (D)
(D) 11. (B) 12. (D)
(D) 13. (B) 14. (A)
15. (D)
(D) 16. (A) 17. (A) 18. (C)
(C) 19. (C)
(C) 20. (A) 21. (C)
(C)
22. (D)
(D) 23. (C)
(C) 24. (C)
(C) 25. (B) 26. (C)
(C) 27. (D)
(D) 28. (D)
(D)
29. (C)
(C) 30. (ACD) 31. (BCD) 32. (BD) 33. (ABD) 34. (BD) 35. (CD)
26. (ABC) 37. (AD) 38. (BCD) 39. (ABCD)
PART # II
1. (c) [Fe(CO)5], Pentacarbonyliron(0)
(d) [Fe(C2O4)3]3 ,
(d)  –
Trioxalatoferrate(III) OR Tris(oxalato)ferrate(III)

(e)
(e) [Cu(NH3)4]SO4, Tetraamminecopper(II) su
sulphate

(f)
(f) Na[Cr(OH)4], Sodium tetrahydroxidochromate(III)

(g)
(g) Co(gly)3, Triglycinatocobalt(III) OR Tris(glycinato)cobalt(III)
(h)
(h) [Fe(H2O)5(SCN)] , 2+
Pentaaquathiocyanato –S –iron(III)

(i) K2[HgI4], Potassium tetraiodidomercurate(II)

(j) Co[Hg(SCN)4], etrathiocyanato –S –mercurate(II)

Cobalt(II) tte

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 COORDINATION COMPOUNDS

(k) Fe4[Fe(CN)6]3, Iron(III) he

hexacyanidoferrate(II)

(l) K3[Co(NO2)6], Potassium hexanitrito –N –cobaltate(III)

(m) [Ni(dmg)2], Bis(dimethylglyoximato)nickel(II)

(n)
(n) K2[PtCl6], Potassium hexachloridoplatinate(IV)

(o) Na2[Fe(CN)5NO+],
(o) Sodium pentacyanidonitros
rosoniumfe
mferra
rrate(II)

(p) [Fe(H2O)5(NO+)]SO4,
(p) Pent
Pentaa
aaqu
quan
anit
itro
roso
soni
nium
umir
iron
on(I
(I)) sulp
sulpha
hate
te

(q) [Cu(CN)4]3 ,
(q)  –
Tetracyanidocuperate(I)
2. (a) Diamminetriaquahydroxidochromium(III) ni nitrate [Cr(NH3)2(H2O)3(OH)](NO3)2
(b) Tetrakis(pyridine)platinum(II) tetraphenylborate(III) [Pt(Py)4][B(ph)4]2
(c) Dibromidotetracarbonyliron(II) [Fe(Br)2(CO)4]
(d)
(d) Tetraammi
etraamminec
necoba
obalt(
lt(III)-3-amido-3-hydroxidobis(ethylenediamine
III)- -hydroxidobis(ethylenediamine or ethane-1, 2-diamine)cobalt(III) chloride

(e) Ammonium diamminetetrakis(isothiocyanato)chromate(III). (NH4)[Cr(NH3)2(NCS)4]

(f) Pentaamminedinitrogenruthenium(II) chloride [Ru(NH3)5N2]Cl2
(g) Bis(cyclopentadienyl)iron(II) [Fe( 1 5 –C5H5)2]
(h) Barium dihydroxidodinitrito-O-oxalatozirconate(IV) Ba[Zr(OH)2(ONO)2(ox)]
(i) Tetrapyridineplatinum(II) tetrachloridoplatinate(II) [Pt(py)4][PtCl4]
(j)
(j) Tetraamm
etraammineineaqu
aquaco
acobal
balt(I II)-3-cyanidotetraamminebromidocobalt(III)
t(III)- [(NH3)4(H2O)Co –CN –Co(NH3)4Br]4+

3. (a) ii < i < iv < iii. (b)

(b) (i) 6 (ii) 2 (iii) 1

4. Complex Geometry Hybridisation Number of unpaired electrons(n) Mag. moment

CN =2
(a) [Ag(NH3)2]+ Linear sp 0 0
 –
(b) [Cu(CN)2] Linear sp 0 0
 –
(c) [AuCl2] Linear sp 0 0
CN = 4
(d) [PtCl2(NH3)2] Square Planar dsp2 0 0
(e) [Zn(C N)4]2
Zn(CN)  –
Tetrahedral sp3 0 0
(f) [Cu(CN)4]3  –
Tetrahedral sp3 0 0
(g) [MnBr4]2  –
Tetrahedral sp3 5 5.92 BM
(h) (NH3)4]2+
[Cu(NH Square Planar dsp2 1 1.73 BM
(i) [CoI4]2 –
Tetrahedral sp3 3 3.87 BM
CN = 6
(j) [Mn(CN)6]3  –
Octahedral d2sp3 2 2.83 BM
(k) (NH3)6]3+
[Cr(NH Octahedral d2sp3 3 3.87 BM
(l) [Fe(CN)6]3  –
Octahedral d2sp3 1 1.73 BM
(m)
(m) [Ir(NH3)6]3+
[Ir(NH Octahedral d2sp3 0 0
(n) [V(CO)6] Octahedral d2sp3 1 1.73 BM
(o) [Fe(H2O)6]2+ Octahedral sp3d2 4 4.90 BM
(p) [MnCl6]3  –
Octahedral sp3d2 4 4.90 BM

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 COORDINATION COMPOUNDS
5. (i) H12O6Cl3Cr
A should be [Cr(H2O)6]Cl3 because it is not reacting with H2SO4 if there would have some moles of water outer the
coordination sphere then it will be reacting with H2SO4
(B) weight of H12O6Cl3Cr = 266.5
6.73
266.5 × = 17.96 5 18 (H2O weight)
100
It means one mole of H2O in B complex outer the coordination sphere
B = [Cr[H2O]5Cl]Cl2.H2O
13 .5
(C) 266.5 ×
100
5 36 (2H2O weight)
It means C = [Cr(H2O)4Cl2]Cl.2H2O
(ii) A = [Cr (H2O)6]Cl3 ; B = [Cr(H2O)5Cl]Cl2.H2O ; C = [Cr(H2O]4Cl2]Cl.2H2O
(iii) EAN = 33
(iv) C  – 1 mole AgCl ppt; B  – 2 mole AgCl ppt; A  – 3 mole AgCl ppt
6. (i) [Cr(NH3)4Cl Br]Cl  –
 #$  AgCl 6 (white) ; soluble in dilute NH3.
[Cr(NH3)4Cl Br]+ + Cl ; Ag+ + Cl  # 
 #$  –

[Cr(NH3)4Cl2]Br [Cr(NH3)4Cl2]+ + Br  –
;  #$  AgBr 6 (yellow) ; soluble in conc. NH 3.
Ag+ + Br  # 
 #$
 –

So, A = [Cr(NH3)4Cl Br]Cl and B = [Cr(NH3)4Cl2]Br.

(ii) In both complexes chromium is in +3 oxidation state. Chromium with 3d3 configuration has 3 unpaired
electrons with weak field as well as strong field ligand. So, the hybridisation scheme is as follow :

(iii) 3 = n (n 7 2)  = 15 (iv) EAN = 24  – 3 + 12 = 33 (v) Yes, both have two ions per formula unit.
(vi) AgCl + 2NH3  [Ag(NH3)2]Cl ; AgBr + 2NH3  [Ag(NH3)2]Br

 – – 2+ 2+
edta

7. (a) Cr

Ru

en

2+
[Ru(en
[Ru(en)) ] ena
enant
ntio
iome
mers
rs
[Cr(edta)]
[Cr(edta)] enantiom
enantiomers
ers 3
 –

Cl
+

Pt

dien

+
[Pt(dien)]

diethylenetriamine dien NH2CH2CH2NHCH2CH2NH2 tridentate

nor [Ru(en)3]2+ has a mirror plane or a centre of inversion; so both are chiral (they also have
 –
Neither [Cr(edta)]   nor
no higher Sn axis); [Pt (dien)Cl]+ has a plane of symmetry and hence is achiral.
(b) Carbonylhydridobis(trimethylphosphine)irridium(I).
Carbonylhydridobis(trimethylphosphine)irridium(I).
!r is in +1 oxidation state; 5d8 configuration has higher CFSE and thus the complex is square planar.

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 COORDINATION COMPOUNDS

5d 6s 6p
[!rH(CO)(PMe 3)2]
2
dsp hyb
hybrid
ridisa
isatio
tion
n
Geometry = Square planar
Magnetic moment = O (all electrons are paired).
8. cis, trans and optical isomers are possible.

9. (a)
(a) There areare three
three constitu
constitution
tional
al isomers
isomers
(i) [Ru(NH3)5(NO2)]Cl (ii) [Ru(NH3)5Cl](NO2) or [Ru(NH3)5Cl]ONO (iii) [Ru(NH3)5 ONO]Cl
(i) & (ii) are ionisation isomers
(i) & (iii) are linkage isomers

(b) (i) (ii) (iii)

(iv) (v) (vi)

10. Diastereisomers are stereisomers which are not enatiomers.

(a)
(a)

Both cis and trans isomers do not show

s how optical activity
activity because of the presence of plane and centre of symmetries.
(b) It will not exhibit geometrical isomerism
isom erism as it exists only in one form as given below.
below.

(c) In tetrahedral geometry all positions are adjacent to each other so it will not exhibit geometrical isomerism.
(d) In square planar geometry
geometr y there is plane of symmetry. So it does not show optical isomerism.

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 COORDINATION COMPOUNDS

(e) It will not exhibit geometrical isomerism

isom erism as it exists only in one form as given below.
below.
SCN
SCN
en Co
3+

SCN
SCN

(f) Cr(NH3)2(H2O)2Cl2]+ is of Ma2b2c2 type which has following isomeric forms.

(aa)(bb)(cc)
(aa)(bc)(bc)
(bb)(ac)(ac)
(cc)(ab)(ab)
(ab)(ac)(bc)

(g)
(g)

11. (a) No ; (b) Yes

Yes ; (c) Yes
Yes ; (d) Yes ; (e) Yes
Yes ; (f) No.

12. 8 Electronic distribution in a tetrahedral d6 ion

t2g

"t Number of unpaired electrons = 4

eg

8 Electronic distribution in square planar d7 ion

dx2 – 
 y
 y
2

dxy Number of unpaired electron = 1

2
dz

dyz dzx

13. 21 14. 5 15. 2 16. 4 17. 84 18. 12 19. 0

20. 5 21. 8 22. 3 23. 0 24. 5 25. 2 26. 0
27. 5 28. 5

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 COORDINATION COMPOUNDS

EXERCISE # 3 
PART
PART # I
1. In [Co(NH3)6]3+, the oxidation state of cobalt is +3 and coordination number is 6. So

Co3+ ion
 ion

NH3 is stronger field ligand. So it compels for the pairing of electrons. T hen

[Co(NH3)6]3+

d2sp3 - hybridisation
Thus with 6 coordination number, the complex [Co(NH3)6] is octahedral as given
giv en below.

In [Ni(CN)4]2 , the oxidation state of nickel is +2 and coordination number is 4. So

 –

Ni2+
 –
CN  is stronger field ligand. So it compels for the pairing of electrons. T hen

[Ni(CN)4]2  –

dsp2 - hybridisation
Thus with 4 coordination number four, the complex is square planar as given below

In [Ni(CO)4], the oxidation state of nickel is zero and the coordination

coor dination number is four. So

Ni (O)

CO is strong field ligand. So it compels for the pairing of electrons; so nickel under goes rearrangem ent. Then

[Ni(CO)4]
sp3 - hybridisation
Thus with 4 coordination number, the complex is tetrahedral as given below.
below.

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2. (A)

3. As form(A) gives white precipitate with AgNO 3 solution and precipitate is readily soluble in dilute aqueous
 –
ammonia, the complex
com plex must be having the Cl  ion in the ionisation sphere. Hence(A) must be having the formula
+  –
[Cr(NH3)4ClBr] Cl .
Ag+ + Cl $ AgCl 6 (white).
 –

AgCl + 2NH3 $ [Ag(NH3)2]+Cl  (soluble complex). –

Similarly form(B) gives pale yellow precipitate with AgNO

AgNO3 and precipitate is soluble in concentrated ammonia,
the complex must be having the Br  in the ionisation sphere. Hence(B) must be having the formula [Cr(NH3)4Cl2]+Br .
 –  –

Ag+ + Br $ AgBr 6 (pale yellow).

 –

AgBr + 2NH3 $ [Ag(NH3)2]+ Br (soluble complex).

In both complexes, the chromium is the central metal ion with +3 oxidation state. In both, the ammonia is a
strong field ligand so it compels for pairing of electrons. Thus,
T hus,

[Cr(NH3)4ClBr]+   or
or [Cr(NH3)4Cl2]+

As itit contai
contains
ns three
three unpa
unpaire
ired
d elect
electron
rons,
s, So, 3 = 3(3 7 2)  = 3.872 B.M.

4. In[NiCl4]2  nickel is in+2 oxidation state and Cl  is weak field ligand. So,
 –  –

[Ni(Cl)4]2  –

3 = n(n 7 2)  = 2(2 7 2) = 2.82 B.M. ; n = No. of unpaired electrons.

Hence with coordination number four, the structure is

Tetrahedral

In[Ni(CN)4]2  nickel is in+2 oxidation state and CN  is strong field ligand, So it compels for pairing of electrons.
 –  –

Then,

[Ni(CN)4]2  –

As all electrons are paired so diamagnetic.

Hence with coordination number four, the structure is

Square planar

5. Let n is the number of unpaired electron in the chromium ion.

Since 3 = n(n 7 2) or 1.73 = n(n 7 2)  B.
 B.M. or 1.73 × 1.73 = n2 + 2n.
Hence n = 1.
1.

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 COORDINATION COMPOUNDS
 –
As the CN  and NH3 are strong fields ligands, they compel for pairing of electrons. So,

[Cr(NO)(CN)4(NH3)]2 =  –

chro mium is +1 (having 3d5 configuration). So according

Hence, the oxidation state of chromium accord ing to charge on the complex
NO should be NO  and the structure of this complex is octahedral with d2sp3 hybridisation as given below
+

According to IUPAC nomenclature its name is :

Potassium amminetatracyanidonitrosoniumchromate(I) OR
Potassium amminetatracyanidonitrocyliumchromate(I).

6. (D)
(D) 7. (C)
(C)

8. Ni2+ + 2dmg  #  #  #   # $  [Ni(dmg)2] 6 (bright red).

NH 4 OH

It acquires stability through chelation and intra molecular H-bonding.

In [Ni(dmg)2] the nickel is in +2 oxidaiton state and to have square planar geometry
geom etry because of chelation the
pairing of electrons takes place. So

[Ni(DMG) 2]

As all electrons are paired, so complex is diamagnetic. Nickel with coordination number four will have the
structure
structur e as given below.
below.

O -------- H  –  O
 O

CH 3  –  C
 C = N N = C  –  CH
 CH3
+2
Ni
H 3C  –  C
 C = N N = C  –  CH
 CH3

O  –  H
 H -------- O

rosy red ppt

9. (A)
SCN 0 0
10. (a) Fe3+  #  # # 
 # $  blood red[Fe((H2O)5(SCN)]2+ (A)
 (A) # F ( excess)
 # #  # # $  colourless(B) [Fe(F6)]3  + SCN  + 5H2O.  –  –

(Excess )
(A) Pentaaquathiocyanato-S-iro
Pentaaquathiocyanato-S-iron(III)
n(III) ; (B) Hexafluoridoferrate(III)
Hexafluoridofe rrate(III)
3+ 1, 1, 1 1,1  –
(b) Fe CFSE electron configuration, t2g eg ; as F  being weak field ligand does not compel for pairing of
electrons. So it contains five unpaired electrons.
 So, 3 = 5 (5 7 2)  = 5.93 B.M.
 The magnetic moment
mom ent value of B is 5.93 B.M.
11. (A) 12. (A) 13. (C)
(C) 14. (C)
(C) 15. (B)
16. (A)  – p, q, s ; (B)  – p, r, s ; (C)  – q, s ; (D)  – q, s 17. (C)
(C) 18. (B) 19. (B) 20. (A)
21. (C), (D) 22. (A) 23. (C)
(C) 24. (B) 25. (B) 26. 3 27. (B)
28. (C)
(C) 29. (A) 30. (D)
(D) 31. (C)
(C)

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 COORDINATION COMPOUNDS

PART # II
1. (2)
(2) 2. (2), (3) 3. (3)
(3) 4. (3)
(3) 5. (4)
(4) 6. (2)
(2) 7. (4)
(4)
8. (1)
(1) 9. (4)
(4) 10. (1)
(1) 11. (4)
(4) 12. (4)
(4) 13. (2)
(2) 14. (3)
(3)
15. (1)
(1) 16. (1)
(1) 17. (2)
(2) 18. (4)
(4) 19. (2)
(2) 20. (3)
(3) 21. (1)
(1)
22. (2)
(2) 23. (3)
(3) 24. (4)
(4) 25. (3)
(3) 26. (1)
(1) 27. (1)
(1) 28. (2)
(2)
29. (3)
(3) 30. (3)
(3) 31. (2)
(2) 32. (3)
(3)

EXERCISE # 4 
1. (i) [Co(NH3)4(H2O)2]Cl3 (ii) K2[Ni(CN)4] (iii) [Cr(en)3]Cl3
 –
(iv) [Pt(NH3)BrCl(NO2)] (v) [PtCl2(en)2](NO3)2 (vi) Fe4[Fe(CN)6]3

2. (i) Hexaamminecobalt(III) chloride

(ii) Pentaamminechloridocobalt(III) chloride
(iii) Potassium hexacyanoferrate(III)
(iv) Potassium trioxalatoferrate(III)
(v) Potassium tetrachloridopalladate(II)
(vi) Diamminechlorido(methanamine)platinum(II)
Diamminechlorido(methanamine)platinum(II) chloride

3. (i) Both geometrical (cis-, trans-) and optical isomers for cis can exist.
(ii) Two optical isomers can exist.
(iii) There are 10 possible isomers. (Hint: There are geometrical, ionisation and linkage isomers possible).
(iv) Geometrical (cis-, trans-) isomers can exist.

4. The ionisation isomers dissolve in water to yield different ions and thus react differently to various reagents :
[Co(NH3)5Br]SO4 + Ba2+ $ BaSO4 (s)
[Co(NH3)5SO4]Br + Ba2+ $ No reaction
[Co(NH3)5Br]SO4 + Ag+ $ No reaction
[Co(NH3)5SO4]Br + Ag+ $ AgBr (s)

6. 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.

 –
7. In presence of CN , (a strong ligand) the 3d electrons pair up leaving only one unpaired electron. The hybridisation
is d2sp3 forming inner orbital complex. In the presence of H2O, (a weak ligand), 3d electrons do not pair up. TheT he
hybridisation is sp3d2 forming an outer orbital complex containing
cont aining five unpaired electrons, it is strongly paramag-
netic.

8. In the presence of NH3, the 3d electrons pair em pty to be involved in d2sp3 hybridisation

pa ir up leaving two d orbitals empty
forming inner orbital complex in case of [Co(NH3)6]3+. In Ni(NH3)62+, Ni is in +2 oxidation state and has d 8
configuration, the hybridisation involved is sp3d2 forming outer orbital complex.

9. For square planar shape, the hybridisation is dsp2. Hence the unpaired electrons in 5d orbital pair up to make
one d orbital empty for dsp2 hybridisation. Thus there is no unpaired electron.

11. The overall dissociation constant is the reciprocal of overall stability constant i.e. 1/ 94 = 4.7 × 10 14
 –

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