Coordination Compounds 429

29 Coordination Compounds
QUICK LOOK  Coordination compounds: Those addition compounds
which retain their identity (i.e., doesn’t lose their identity) in
Molecular or addition compounds are formed when solution are called co-ordination compounds. For example,
stoichiometric amounts of two or more stable compounds join when KCN solution is added to Fe(CN) 2 solution, the
together. These fall into two categories: species formed, no longer gives tests of Fe 2 and CN  .
(a) Those which lose their identity in solution.
Fe(CN2) 4KCN 
Fe(CN).4KCN or
(b) Those which retain their identity in solution.
An aqueous solution of carnallite shows the properties of K 4 [Fe(CN) 6(aq.)     4K  (aq.) [Fe(CN 6)(aq)]
4:1complex

K  ,Mg 2 and Cl  ions. Potassium alum solutions similarly

Oth er examples are, [Cu(NH 3) ]SO
4 (aq.)
4    
 3 2
show the properties of K ,Al and SO ions. They are called
4
[Cu(NH 3) 4] 2 (aq.) SO 24(aq.)

K 2 [Zn(CN 4 )](aq.)
double salts and exist only in the crystalline state. The other 1:1complex

two examples of addition compounds behave in a very different     2K  (aq.) [Zn(CN) 4] 2 (aq.)
2 :1complex
way from the double salts. When dissolved they do not form
2  A lso, coordination compound is defined as species in which
Cu 2  , or Fe and CN ions, but instead give more complicated
metal atom or ion is attached to group of neutral
2
structures—the cuproammonium ion [Cu(H 2O) 2 (NH3 ) 4] and molecules/ions by coordinate covalent bonds.
the ferrocyanide ion [Fe(CN) 6] 4. These are complex ions and  Ligand: It is an ion or molecule capable of donating a pair
of electrons to the central atom via a donor atom. The
exist are a single entity. Complex ions are indicated by square
neutral molecules, anions or cations which are directly lined
brackets. Molecular compounds of this type are called co-
with central metal atom or ion in the coordination entity are
ordination compounds. Coordination compounds are the
called ligands. Ligands may be simple ions such as Br  ,
compounds in which the central metal atom is linked to ions or
small molecules such as H 2O or NH3, larger molecules
neutral molecules by coordinate bonds, e.g.
2 such as H 2 NCH 2CH 2NH 2 or N(CH 2CH 2NH 2) 3 or even
Cr  H 2O 5Cl  . If the species thus formed as given above
macromolecules such as proteins.
carries positive charge, it is called a complex ion. When a ligand is attached to a metal ion through a single donor
 Double salts: Those addition compounds which lose their atom, as with Cl  ,H 2O or NH3, the ligand is said to be
identity in solution are called double salts. For example,
unidenate. Similarly when a ligand is bond through two dononr
when K 2SO 4 solution is added to Al 2(SO 4) 3 solution, atoms, as in H 2 NCH 2CH 2NH 2 (ethane-1, 2-diamine) or
2
species formed gives tests of K  ,Al 3 and SO4 ions. C 2 O 42 (oxalate), the ligand is said to be bidentate and when
K2SO4 Al2(SO4)3 24H2O 
K 2SO 4.Al 2(SO 4) 3.24H 2O several donor atoms are present in a single ligand as in
N(CH 2CH 2NH 2) 3 or ethylene-diaminetetraacetic acid
        (aq.) (aq.)  2Al3(aq).  4SO24(aq.)
(EDTA), the ligand is said to be polydentate.
Other Examples
Classification of Ligands: There are several ways to
Ferric alum: K 2SO 4.Fe 2(SO )4 .24H
3 O2
classify ligands and these are discussed as under:
C hrome alum: K 2SO 4.Cr2(SO 4) .24H
3 O
2  Based upon charges
C arnallite: KCl.MgCl2.6H 2O (a) Neutral ligands: H 2 O,NO,CO,C H 6 ,6 etc.

 
Mohr’ s salt: (NH 4) 2SO .FeSO
4 6H
4 O2 (b ) Positive ligands: N O and NH 2  NH 3
T utton salt: M 2SO 4,CuSO .6H O[M 
Na,K]    
4 2 (c) Negative ligands: Cl ,NO ,CN
2 ,OH
430 JEE-Main and Advanced Chapter-wise Solved Papers: Chemistry
 Based upon denticity of the ligand: The number of (b ) Non-classical or -acid or -acceptor ligand: These
donations accepted by a central atoms from a particular ligands not only donate the lone pair of electrons to the
ligand is known as the denticity of the ligand. Ligands may central atom but also accept the electron cloud from the
be classified as follows based on their denticity: central atom in their low-lying vacant orbitals. This kind of
Monodentate: Only one donation is accepted from the back donation is known as ‘synergic effect’ or ‘synergic
ligand. bonding’.
Example: H 2 O,NO, CO, NH3, CO32 ,Cl , etc. Example: Co,CN,NO,PF ,PR
3 3
(R  H,Et, Ph...),
Bidentate: Ligands with two donor atoms, e.g. ethyl- C2 H 4 ,C 2H 4 ,CO 2 ,etc.
2
enediamine, C2O (oxalate ion) etc. Two donations are
4 (a) In case of CO, the back donation to the * orbital of
accepted from the ligand. central atom may be depicted as:
 Chelating ligand: Multidentate ligand simultaneously co- π*
ordinating to a metal ion through more than one site, a : M=C=O
M
ligand that can form a ring structure with the central atom is
called a chelating ligand. All polydentate ligands are the π*
Figure: 29.1
example of chelating ligands. Chelated complexes are more
stable than similar complexes with monodentate ligands as By valence bond or molecular orbital theory, it is well
dissociation of the complex involves breaking two bonds understood that the bond order of C—O bond decreases but
rather than one. However, it must be noted that the C—O bond length must increase due to synergic effect.

NH 2NH 2 and N (CH 2 CH 2) N
3 cannot act as chelating Similarly, as CN and N O are isoelectronic with CO, so
ligands due to the formation of three membered ring and back donation takes place in these species also in the
locked structure, respectively. π * orbitals and the same conclusion can be drawn for the
H 2C— NH O  C—O : bond order and bond lengths.
2
Example: | | (b) In case of PR 3, the back donation may be depicted as:
H 2C— NH O  C—O :
2 Vacant 3d orbital accepts
Ethylene diamine Oxalateion
the back donation
 Ambidentate ligand: A ligand that may have more than
one kind of donor sites but at a time only one kind of donor M : P
site is utilised for donation is called as ambidentate ligand.
Ligands which can ligate through two different atoms
Figure: 29.2
present in it. Examples of such ligands are the NO2 (c) In case of C 2H4, the back donation may be depicted
 
and SCN ions. NO ion can coordinate through either the using the example of Zeise’s salt.
2
H
nitrogen or the oxygen atoms to a central metals atom/ion.
*
Similarly, SCN  ion can coordinate through the sulphur or Cl Cl π C H
nitrogen atom. Such possibilities give rise to linkage Pt
isomerism in coordination compounds. For example, Cl H
π* C
O
M  N nitrito-N H
O
Figure: 29.3
 O — N  O nitrito-O
M 
Here the back donation is accepted in the* orbitals of C—C
M 
 SCN thiocyanato or thiocyanato-S bond. Hence, the bond order of C—C bond decreases and the
M 
 NCS isothiocyanato or thiocyanato-N bond length increases as compared to free C 2H4 molecule. Due
 Based upon bonding interaction between the ligand and to back bonding C 2H4 molecule loses its planarity. Similarly,
the central atoms C2H2 molecules loses its linearity not the planarity.
(a) Classical or simple donor ligand: These ligands only
 IUPAC Nomenclature of complex compounds: In order
donate the lone pair of electrons to the central atom. For
to name complex compounds certain rules have been
2    3
example, O ,OH ,F ,NH ,NH
2 ,N
3 ,etc. framed by IUPAC. These are as follows:
Coordination Compounds 431
 The positive part of a coordination compound is named first [(NH 3)] 5Co NH 2 Co(NH ) 3](NO
5 ) 3 5
 -amidobis [pentaamminecobalt (III)] nitrate
and is followed by the name of negative part.
 The ligands are named first followed by the central metal. [(NH 3) 5Co OH 
Co(NH ) 3]Cl
5 5
 - hydroxobis [pentaamminecobalt (III) ] chloride
The prefixes di-, tri-, tetra-, etc., are used to indicate the
[(CO) 3Fe(CO) 3Fe(CO) ]3
number of each kind of ligand present. The prefixes bis tri-  carbonylbis [tricarbonyliron (0)]

(two ligands), tris (three ligands), etc., are used when the [Be O(CH COO) ]
4 3 6
ligands includ a number e.g., dipyridyl, bis hexa --acetato(O,O')-4 oxotetraberyllium(II)

(ehylenediamine).  If any lattice component such as water or solvent of

 In polynuclear complexes, the bridging group is indicated in crystallisation are present, these follow the name and are
the formula of the complex by separating it from the rest of preceded by the number of these groups (molecules of
the complex by hyphens. In polynuclear complexes (a solvent of crystallisation) in Arabic numerals.
complex with two or more metal atoms), bridging ligand [Cu(H 2O) 4]SO .H
4 O
2
Tetraaquacopper(II)sulphate1 water
(which links two metal atoms) is denoted by the prefix 
[Cr(H O) Cl ]Cl.2H O
2 4 2 2
before its name. tetraaquadichlorochromium (III( chloride2-water

 Naming of ligands: The different types of ligands i.e.  Following punctuation rules should also be followed while
neutral, negative or positive are named differently in a writing the name of the complex compounds. The name of the
complex compound. When a complex species has negative complete compound should not start with a capital letter, e.g.,
charge, the name of the central metal ends in – ate. For [Cu(NH ) ]SO 3 4 4
some elements, the ion name is based on the Latin name of Tetraamminecopper (II) sulphate (Correct)
Tetraamminecopper (II) sulphate (Incorrect)
the metal (for example, argentate for silver). Some such
T he full name of the complex ion should be written as one
Latin names used (with the suffix – ate) are given below:
word without any gap. There should be a gap between the
Fe Ferrate Cu Cuperate cation and anion in case of ionic complexes. The full name
Ag Argentate Au Aurate of non-ionic complexes should be written as one word
Sn Stann ate Pb Plumbate without any gap.
 Drawbacks of valence bond theory
 Point of attachment in case unidentate ligands with (a) The classification of complexes as ionic or outer orbital
more than coordinating atoms (ambidentate ligands) : and covalent or inner orbital is arbitrary. It could not
The point of attachment in case of unidentate ligands with explain why some complexes of metal ion use inner orbitals
more than one coordinating atom is either indicated by (d 2sp 3, low spin complexes) whereas some other make high
using different names for the ligands (e.g, thiocyanato and spin complexes (sp 3d 2).
isothiocyanato) or by placing the symbol of the donor
(b) The explanation offered in the VBT for many complexes
atom attached, the name of the ligand separated by a
of Cu(II) involving promotion of a 3d electron to a 4p
hypen.
orbital was unsatisfactory, as explained earlier. It can’t
(NH ) [Cr(SCN) ]
4 3 6 (NH ) [Pt(NCS) ]
4 2 6
predict effectively whether a four coordinated complex is
Ammonium hexathioxyanato -S-chromate (III) Ammonium hexathiocyanato -N-platinate (IV)
or or tetragonal or square planar e.g., [Cu(NH 3) 4] 2  is suggested
Ammonium hexathiocyanatochromate (III) Ammonium hexaisothiocyanatoplatinate (IV)

 Name of the bridging groups: If a complex contains two to have sp3 configuration by Valence Bond. Theory, but X-
or more central metal atoms or ions, it is termed as rays study shows its geometry as square planar, i.e., dsp 2.
polynuclear. In certain polynuclear complexes, ligands may ( c) It doesn’t explain the variation of magnetic properties of
link the two metal atoms or ions. Such ligands which link complex with temperature.
the two metal atoms or ions in polynuclear complexes are (d) It doesn’t explain or predicted any distortion in symmetrical
termed as bridge ligands. These bridge ligands are separated complexes. A number of assumptions are involved.
from the rest of the complex by hyphens and denoted by the (e) There is no quantitative interpretation of magnetic data.
prefix  . If there are two or more bridging groups of the (f) It has nothing to say about the spectral properties of
same kind, this is indicated by di- , tri  , etc. coordination compounds.
432 JEE-Main and Advanced Chapter-wise Solved Papers: Chemistry
(g) It does not give a quantitative interpretation of the there are six wave functions but can be written for orbitals
thermodynamic or kinetic stabilities of coordination having the typical four-lobed form (d xy and d x 2  y2 , for
compounds.
example), but there can be only five d-orbitals having any
(h) It does not distinguish between strong and weak ligand.
physical reality, therefore, one of them the "d z2 " orbital is
 Crystal field theory: The crystal field theory, first proposed
by Hand Bethe in 1929 to explain the colour and magnetic conventionally regarded as a linear combinations of two
properties of some solid crystalline salts of metals. It was others, the d z 2  y2 and d z2  x 2.
also applied to interpret the electronic spectra of transition Thus these latter two orbitals have no independent
metal complexes. The principal qualitative aspects of the existence, but the d z 2 can be thought of as having the
crystal field theory (CFT) may be summarized as follows.
average properties of the two shown in figure 29.4.
(a) It is a hypothetical modal in which the ligands are
Therefore, since both have high electron density along
imagined to be point negative charges (either from the net
the z-axis, the d z 2 orbital has a large fraction of its
negative charge on the ligand or from the negative end of
the ligand dipole arising from the lone pair of electrons on electron density concentrated along the same axis. Also,
its donor atom). the ionic ligands (e.g., F –,Cl– etc.) are since one of the component wave function (d z 2  x 2) has
regarded as negative point charges, while neutral ligands lobes the x-axis and the other (d z 2  y2) along the y-axis,
(e.g., H2O,NH3 etc) are regarded as dipoles.
the resultant d z 2 orbital has a tours of electron density in
(b) The bonding between the central metal cation and
ligands is purely electrostatic or coulombic in nature. The the xy plane, which is often referred to as “doughnut or
theory now considers only the electrostatics interaction collar”. It will be better to divide the set of d orbitals in
between a metal and the ligands. This may be considered in two groups:
z
two steps: (a) electrostatics attraction between the positive
nucleus of the metal and the negatively charged electrons of
the ligands (imagined as point charges): (b) electrostatic dz2 x2 x
z
repulsion force between the electrons in the valence shell of
the metal and the ligand electrons.
z x
(c) The arrangement of the ligands around the central metal
ion is such that the repulsion between these negative points y
is minimum.
(d) Splitting of d-orbital energies: The five d-orbitals in an
dy2z2
isolated gaseous metal atom/ion are degenerate i.e., they y
have equal energy. If a spherically symmetric field of Figure: 29.4
negative charges is placed around the metal, the orbitals will (a) The orbitals in which lobes lie along the axes (d x 2  y2 .d z2 ):
remain degenerate, but all of them will be raised in energy
reffered to as "e g " orbitals in Octahedral symmetry and “e”
as a result of repulsion between the negative field and the
negative electrons in the orbitals. If the field results from orbitals in Tetrahedral symmetry. (Also called as doubly
the influence of real ligands (either anions or the negative degenerate orbitals).
ends of dipolar ligands, such as NH 3 or H 2 O), the symmetry (b) The orbitals in which lobes lies in between the axes
(d xy ,d yz,d zx): reffered to as "t 2g " orbitals in Octahedral
of the field will be less than spherical and the degeneracy of
the d-orbitals will be removed. It is this splitting of d orbital symmetry and "t 2 " orbitals in Tetrahedral symmetry. (Also
energies and its effects that form the basis of crystal field called triply degenerate orbitals.)
theory.  Crystal field splitting of d-orbitals in octahedral
 Geometrical relationship of the d-orbitals: There is no complexes: Assume six ligands symmetrically positioned
unique way of representing the five d-orbitals, but the most along the Cartesian axes, with metal atom at origin as
convenient representations are shown in figure 29.4. In fact, shown in the figure 29.5.
Coordination Compounds 433
+z the bary centre of the d-orbitals holds for all complexes,
regardless of geometry. So
–y
C.F.S.E. [ 0.4(n)t 2g 0.6(n')e ]g o 
np
–x
+x
Where n & n’ are number of electron(s) in t 2g & eg orbitals
respectively and  o crystal field splitting energy for
+y octahedral complex. n represents the number of extra
–z electron pairs formed because of the ligands in comparison
Figure: 29.5
to normal degenerate configuration.
N ow there will be repulsion between the electrons of  Isomerism among Coordination Compounds: When the
ligands and that present in the d orbitals and same empirical formula applies to two or more complexes
consequently the energy of the d orbitals will be raised. having different structures, either in atom connectivity or in
However this raise in energy will not be same for every d the orientation of atoms in space, the compounds are
orbital and it can be clearly seen that the "eg " orbtials referred to as isomers. Isomerism in complex compounds
will be raised more in energy due to stronger repulsions may arise in many ways. The number of isomers depend on
the coordination number of the metal and the geometry
than the "t 2g " orbitals. To understand this splitting more
adopted by it and also on the nature of the ligand. In one
clearly we can assume it to be a two step process as
respect such isomerism differs from the isomerism observed
shown in figure.
in carbon compounds. Actually, the stereochemistry of
dx2 y2 ,dz2 coordination compounds is more varied since metals
eg involve much larger number of orbitals (s, p and d) whose
0.6 o energy and spatial distribution are widely different. The
Energy

o
Average energy level
main types within each category may be further classified as
0.4 o (Bary-centre) follows:

t 2g Isomerism
d xy ,d yz,d xz

step I step II Constitutional Isomerism Stereoisomerism

d orbitals in free ion 1. Ionisation 1. Geometrical
2. Hydrate 2. Optical
Figure: 29.6 3. Coordinate
 Step (i): Average energy of the d-orbitals of metal atom/ion 4. Linkage
in a hypothetical spherical crystal field. 5. Polymerisation
 Step (ii): Splitting of d-orbitals of metal atom/ion in 6. Ligand
octahedral crystal field. In the first step, the ligands
approach the central metal, producing a hypothetical Names of Ligands
spherical field which repels all of the d-orbitals to the same (a) Names of anionic ligands (both organic and inorganic) end
extent. In the second, the ligands exert an octahedral field, in –o. The anion names are usually changed accordingly:
which splits the orbital degeneracy. In going from the first —ide 
 ido; —ite  1to. ito.
 ito; —ate 
to the second step, average energy (the bary centre, or Exceptions are halides (halo), hydroxides (hydroxo),
“center of gravity”) of the orbitals must remain constant and peroxides (peroxo) etc.
it is necessary for the two e g orbitals to be the further
(b) Names of neutral and cationic ligands are used without
repelled by 0.6  0 while the three t 2g orbitals are stabilized modification and placed within enclosing mark except for
to an extent of 0.4  0 as shown in figure. This constancy of aqua, ammine carbonyl and nitrosyl.
434 JEE-Main and Advanced Chapter-wise Solved Papers: Chemistry
MULTIPLE CHOICE QUESTIONS 7. The ionization isomer of [Cr(H 2O) 4Cl(NO 2)]Cl is
One and More than One Correct [JEE 2010 P-I]
1. If the bond length of CO bond in carbon monoxide is a. [Cr(H 2O) 4(O N)]Cl
2 2 b. [Cr(H 2O) 4Cl ](NO
2 )2
1.128 Å, then what is the value of CO bond length in c. [Cr(H 2O) 4Cl(ONO)]Cl d. [Cr(H2O)4Cl2(NO2)]H 2O
Fe(CO) 5 ? [JEE 2006]
8. T he complex showing a spin-only magnetic moment of
a. 1.15 Å b. 1.128 Å
2.82 B.M. is [JEE 2010 P-II]
c. 1.72 Å d. 1.118 Å
a. Ni(CO) 4 b. [NiCl 4] 2
2. Among the following metal carbonyls, the C—O bond
order is lowest in [JEE 2007 P-II] c. Ni(PPh 3) 4 d. [Ni(CN) 4] 2

a. [Mn(CO) 6] b. [Fe(CO)5] 9. Geo metrical shapes of the complexes formed by the

c. [Cr(CO) 6] d. [V(CO) 6] reaction of Ni 2  with Cl  , CN  and H 2 O, respectively,
are [JEE 2011 P-I]
3. Bo th [Ni(CO) 4] and [Ni(CN) 4] 2 are diamagnetic. The
a. octahedral, tetrahedral and square planar
hybridization of nickel in these complexes, respectively, b. tetrahedral, square planar and octahedral
are [JEE 2008 P-II] c. square planar, tetrahedral and octahedral
a. sp 3,sp 3
b. sp 3, dsp 2 d. octahedral, square planar and octahedral
c. dsp 2,sp 
d. dsp 2 ,dsp 2 10. Among the following complexes (K–P)
4. T he compound(s) that exhibit(s) geometrical isomerism K 3 [Fe(CN) 6]( K), [Co(NH 3) ]Cl
6 3( ),
L
is(are) [JEE 2009 P-I] Na 3 [Co(oxalate)3]( M), [Ni(H 2O) 6]Cl 2 (N ),
a. [Pt(en)Cl 2] b. [Pt(en) 2]Cl 2 K 2 [Pt(CN) 4 ]( O) and [Zn(H 2O) 6](NO ) 3 (2 ) P
Follo wing compounds are diamagnetic.
c. [Pt(en) 2Cl ]Cl
2 2 d. [Pt(NH 3) Cl
2 ]2
[JEE 2011 P-II]
5. T he spin only magnetic moment value (in Bohr magneton a. K, L, M N b. K, M, O, P
units) of Cr(CO) 6 is [JEE 2009 P-II] c. L, M, O, P d. L, M, N, O

a. 0 b. 2.84 11. NiCl2 {P(C2 H5 )2 (C6H5 )}2 exhibits temperature dependent

c. 4.90 d. 5.92 magnetic behavior (paramagnetic / diamagnetic). The
6. The correct structure of ethylenediaminetetraacetic acid coordination geometries of Ni 2+ in the paramagnetic and
(EDTA) is [JEE 2010 P-I] diamagnetic states are respectively. [JEE 2012 P-II]
a. tetrahedral and tetrahedral
HOOC— CH 2 CH 2 —COOH b. square planar and square planar
a. N – CH = CH –N
HOOC— CH 2 CH 2 —COOH c. tetrahedral and square planar
d. square planar and tetrahedral
HOOC COOH
b. N  CH2  CH 2  N 12. Which of the following complex species is not expected to
HOOC COOH exhibit optical isomerism? [JEE Main 2013]
a. [Co(en 3)] 3 b. [Co(en) 2Cl ]2 

HOOC—CH 2 CH2 —COOH 

c. N  CH2 CH 2 N c. [Co(NH 3) 3Cl ]3 d. [Co(en)(NH 3) Cl
2 ]2

HOOC—CH 2 CH2 —COOH

13. C onsider the following complex ions, P, Q and R
2
COOH P  [FeF6 ] 3 , Q  [V(H 2O) ]6 2
and R  [Fe(H2 O)6 ] . The
CH 2 correct order of the complex ions, according to their spin-
d. HOOC—CH 2 | H only magnetic moment values (in B.M.) is
NHC—CH N
H | [JEE Adv. 2013 P-I]
CH 2 —COOH
CH 2 a. R < Q < P b. Q < R < P
HOOC c. R < P < Q d. Q < P > R
Coordination Compounds 435
14. The pair(s) of coordination complexes/ions exhibiting the 21. Addition of excess aqueous ammonia to a pink coloured
same kind of isomerism is(are) [JEE Adv. 2013 P-I] aqueous solution of MCl 2  6H 2O  X  and NH 4Cl gives
a. [Cr(NH 3) Cl]Cl
5 2 and [Cr(NH 3) Cl
4 ]Cl
2 an octahedral complex Y in the presence of air. In
b. [Co(NH3 ) 4Cl 2]

and [Pt(NH 3) 2(H 2O)Cl]  aqueous solution, complex Y behaves as 1 : 3 electrolyte.
2 The reaction of X with excess HCl at room temperature
c. [CoBr2Cl 2] and [PtBr2Cl 2] 2 
results in the formation of a blue coloured complex Z. The
d. [Pt(NH 3) (NO
3 )]Cl
3 and [Pt(NH 3) Cl]Br
3 calculated spin only magnetic moment of X and Z is 3.87
15. T he number of geometric isomers that can exist for square B.M., whereas it is zero for complex Y. Among the
planar [Pt(Cl)(py) (NH3)(NH OH)] 
is (py = pyridine): following options, which statement(s) is(are) correct?
2
[JEE Adv. 2017 P-I]
[JEE Main 2015]
a. 2 b. 3 c. 4 d. 6 a. The hybridization of the central metal ion in Y is d 2sp 3

16. The pair having the same magnetic moment is: b. When X and Z are in equilibrium at 0°C, the colour of
[At. No.: Cr = 24, Mn = 25, Fe = 26, Co = 27] the solution is pink
[JEE Main 2016] c. Z is a tetrahedral complex
2 d. Addition of silver nitrate to Y gives only two equi-
a. [Cr(H 2O) ]6 and [CoCl 4 ]2 
valents of silver chloride
2 2
b. [Cr(H 2O) ]6 and [Fe(H 2O) 6]
2 2
22. H ydrogen peroxide oxidises [Fe(CN)6]4– to [Fe(CN)6]3– in
c. [Mn(H 2O) 6] and [Cr(H 2O) ]6
acidic medium but reduces [Fe(CN)6]3– to [Fe(CN)6]4– in
d. [CoCl 4 ]2  and [Fe(H 2O) 6] 2
alkaline medium. The other products formed are,
17. Which one of the following complexes shows optical respectively. [JEE Main 2018]
–
isomerism? [JEE Main 2016] a. H2O and (H2O + OH )
a. [Co(NH 3) Cl ] b. (H2O + O2) and H2O
3 3
c. (H2O + O2) and (H2O + OH–)
b. cis[Co(en) 2 Cl 2]Cl
d. H2O and (H2O +O2)
c. trans[Co(en) 2 Cl2]Cl (en = ethylenediamine)
23. Diborane (B 2H6) reacts independently with O 2 and H 2O to
d. [Co(NH 3) Cl
4 2]Cl produce, respectively [JEE Main 2019]
18. Am ong [Ni(CO)4 ], [NiCl 4] 2 , [Co(NH3 )4Cl 2]Cl, Na3[CoF6 ], a. HBO2 and H3BO3 b. H3BO3 and B2O3
c. B2O3 and H3BO3 d. B2O3 and [BH4]–
Na 2 O 2 and CsO 2 the total number of paramagnetic
compounds is [JEE Adv. 2016 P-I] 24. The correct order of the spin-only magnetic moment of
a. 2 b. 3 c. 4 d. 5 metal ions in the following low spin complexes,
[V(CN)6]4–, [Fe(CN)6]4–, [Ru (NH 3)6]3+, and [Cr(NH 3)6]2+,
19. Th e geometries of the ammonia complexes of Ni 2  , Pt 2  & is : [JEE Main 2019]
2+ 2+ 3+ 2+
Zn 2  , respectively, are [JEE Adv. 2016 P-II] a. V > Cr > Ru > Fe
a. octahedral, square planar and tetrahedral b. V2+ > Ru3+ > Cr2+ > Fe2+
b. square planar, octahedral and tetrahedral c. Cr2+ > V2+ > Ru3+ > Fe2+
c. tetrahedral, square planar and octahedral d. Cr2+ > Ru3+ > Fe2+ > V2+
d. octahedral, tetrahedral and square planar 25. The ion that has sp 3d2 hybridization for the central atom,
20. On treatment of 100 mL of 0.1 M solution of is : [JEE Main 2019]
– –
a. [ICl2] b. [IF6]
CoCl3 6H 2O with excess AgNO3 1.2 1022 ions are
c. [ICl4]– d. [BrF2]–
precipitated. The complex is [JEE Main 2017]
 O
a. [Co(H 2O) 5Cl]Cl 2 H 26. The calculated spin-only magnetic moments (BM) of the
2
anionic and cationic species of [Fe(H2O)6]2 and [Fe(CN)6],
b. [Co(H 2O) 4Cl ]Cl  O2
22H
2 respectively, are : [JEE Main 2019]
 O2
c. [Co(H 2O) 3Cl ]3 3H a. 4.9 and 0 b. 2.84 and 5.92
d. [Co(H 2O) 6]Cl c. 0 and 4.9 d. 0 and 5.92
3
436 JEE-Main and Advanced Chapter-wise Solved Papers: Chemistry
2
27. Among the following molecules / ions, C ,N ,O ,O
2
2
2
2
2 2
35. The difference in the number of unpaired electrons of a
w hich one is diamagnetic and has the shortest bond metal ion in its high-spin and low-spin octahedral
length? [JEE Main 2019] complexes is two. The metal ion is: [JEE Main 2019]
2+ 2+ 2+
a. Fe b. Co c. Mn d. Ni2+
a. C 22  b. N 22  c. O2 d. O 22 
36. Which of the following tests cannot be used for
28. The correct statement about ICl5 and ICl4 is identifying amino acids? [JEE Main 2019]
[JEE Main 2019] a. Biuret test b. Xanthoproteic test

a. ICl5 is trigonal bipyramidal and ICl is tetrahedral.
4 c. Barfoed test d. Ninhydrin test
b. ICl5 is square pyramidal and ICl4 is tetrahedral. 37. The number of bridging CO ligand (s) and CO-CO bond

c. ICl5 is square pyramidal and ICl is square planar. (s) in CO2(CO)g, respectively are :- [JEE Main 2019]
4
a. 0 and 2 b. 2 and 0
d. Both are is ostructural.
c. 4 and 0 d. 2 and 1
29. Two complexes [Cr(H 2O 6)Cl ]3 (A) and [Cr(NH 3) 6]Cl 3
38. The hydride that is NOT electron deficient is:-
(B) are violet and yellow coloured, respectively. The
[JEE Main 2019]
incorrect statement regarding them is: [JEE Main 2019]
a. B2H6 b. AlH3 c. SiH4 d. GaH3
a. 0 value of (A) is less than that (B).
b. 0 value of (A) and (B) are calculated from the energies 39. The coordination number of Th in K 4[Th(C2O4]4(OH2)2]
2-
of violet and yellow light, respectively. is:- ( C2O4  Oxalato) [JEE Main 2019]
c. Both absorb energies corresponding to their comple- a. 6 b. 10 c. 14 d. 18
mentary colors.
40. Mn 2(CO)10 is an organometallic compound due to the
d. Both are paramagnetic with three unpaired electrons.
presence of : [JEE Main 2019]
30. The complex that has highest cry splitting energy (), is a. Mn —Mn bond b. Mn — C bond
[JEE Main 2019] c. Mn —O bond d. C — O bond
a. K3[CO(CN)6] b. [CO(NH3)5(H2O)]Cl3
41. The pair of metal ions that can give a spinonly magnetic
c. K2[COCl4] d. [CO(NH3)5Cl]Cl2
moment of 3.9 BM for the complex [M(H2O)6]Cl2, is :
31. The metal that form nitride by reacting directly with N 2 of [JEE Main 2019]
2+ 2+
air, is [JEE Main 2019] a. Cr and Mn b. V and Co2+
2+

a. K b. Cs c. Li d. Rb c. V2+ and Fe2+ d. Co2+ and Fe2+

32. Homoleptic octahedral complexes of a metalion 'M 3+' with 42. The magnetic moment of an octahedral homoleptic
three monodentate ligands and L 1, L2, L3 absorb Mn(II) complex is 5.9 BM. The suitable ligand for this
wavelengths in the region of green, blue and red complex is : [JEE Main 2019]
respectively. The increasing order of the ligand strength a. CN– b. NCS–
is: [JEE Main 2019] c. CO d. ethylenediamine
a. L2 < L1 < L3 b. L3 < L2 < L1
43. Which of the following set represent correct formula for
c. L3 < L1 <L2 d. L1 < L2 < L3
Malachinte, Magnetite, Calamine & Cryolite?
33. Wilkinson catalyst is: [JEE Main 2019] [JEE Adv. 2019 P-I]
a. [(Ph3P)3RhCl] (Et = C 2H5) a. CuCO3,Fe2O3, ZnO, Al2O3
b. [(Et3P)3IrCl] b. CuCO3. Cu(OH)2, Fe3O4, ZnCO3, Na3AlF6
c. [(Et3P)3RhCl] c. CuCO3, Fe3O4, ZnCO3 Al2O3
d. [(Ph3P)3IrCl] d. CuCO3. Cu(OH)2, Fe2O3, ZnCO3, Na3AlF6
34. The type of hybridisation and number of lone pair(s) of 44. Identify the option where all four molecules possess
electrons of Xe in XeOF4, respectively, are: permanent dipole moment at room temperature.
[JEE Main 2019] [JEE Adv. 2019 P-I]
a. sp3d and 1 b. sp3d and 2 a. BF3, O3, SF6, XeF6 b. BeCl2, CO2, BCl3, CHCl3
c. sp3d2 and 1 d. sp3d2 and 2 c. SO2, C6H5Cl, H2Se, BrF5 d. NO2, NH3, POCl3, CH3Cl
Coordination Compounds 437
45. 1-Methylethylene oxide  excess
 X, Product ‘X’ will be: a. a = b = c < d b. a < b < c < d
HBr
c. a > b > c > d d. a = b > c > d
[JEE Main P-I 2020]
Br 51. Among the following which will show geometrical
a. b. Br isomerism. [JEE Main P-I 2020]

Br
Br (a) [Ni(NH3) 5Cl]  (b) [Ni(NH 3) ClBr]
4

c. Br d. Br (c) [Ni(NH3) 3Cl]  (d) [Ni(NH 3 ) 2 (NO 2 )2 ]

Br
a. b, d b. a, b
46. The IUPAC name of complex [Pt(NH 3) 2Cl(NH CH
2 )]Cl
3 c. a, b and c d. a, b, c and d
is: [JEE Main P-I 2020]
52. Complex Cr(H 2O) 6Cl n shows geometrical isomerism and
a. Diamminechlorido (amminomethane) platinum(II)
chloride. also reacts with AgNO3 solution. [JEE Main P-I 2020]
b. Diamminechlorido (methanamine) platinum(II) Given: Spin only magnetic moment = 3.8 B.M.
chloride. What is the IUPAC name of the complex?
c. Diammine (methanamine) chlorido platinum(II) a. Hexaaquachromium (III) chloride
Chloride. b. Tetraaquadichloridochromium (III) chloride dihydrate
d. Biasmmine (methanamine) chlorido platinum(II) c. Heaxaquachromium (IV) chloride
chloride. d. Tetraaquadichloridochromium (IV) chloride dihydrate
47. Which of the following statements are incorrect? 53. [PdFClBr1]2 Number of Geometrical Isomers = n. For
[JEE Main P-I 2020]
[Fe(CN)6] n  6, Determine the spin only magnetic moment
(A) Co3 with strong field ligand forms high magnetic
and CFSE (Ignore the pairing energy)
moment complex.
[JEE Main P-I 2020]
(B) For Co3 if pairing energy (P) > o then the complex
a. 1.73 B.M., 2 0 b. 2.84 B.M., 1.6 0
formed will have t 42g , e 2g configuration
c. 0, 1.6 0 d. 5.92 B.M., 2.4 0
(C) For [Co(en) 3] 3  absorbed is less than  absorbed for [CoF6 ]3
54. Given complex [Co(NH 3) 4Cl ]. In it if Cl  Co Cl bond
(D) If o = 18000 cm –1 for Co3 then with same ligands 2

angle is 90º then it is: [JEE Main P-I 2020]

for it t = 16000 cm–1
a. A, D b. B, C c. A, B d. A, B, C, D a. Cis-isomer b. Trans-isomers
c. Meridional and trans d. Cis and trans both
48. In comparison to the zeolite process for the removal of
permanent hardness, the synthetic resins method is: 55. For octahedral Mn(II) and tetrahedral Ni(II) complexes,
consider the following statements :
[JEE Main P-I 2020]
a. less efficient as it exchanges only anions. (I) both the complexes can be high spin.
b. more efficient as it can exchange only cations. (II) Ni(II) complex can very rarely be of low spin.
c. more efficient as it can exchange both cations as well as (III) with strong field ligands, Mn(II) complexes can be
anions. low spin.
d. less efficient as the resins cannot be regenerated. (iv) aqueous solution of Mn(II) ions is yellow in color.
The correct statements are : [JEE Main P-II 2020]
49. Which of the following complex exhibit facial meridional a. (I) and (II) only b. (I), (II) and (III) only
geometrical isomerism? [JEE Main P-I 2020] c. (I), (III) and (IV) only d. (II), (III) and (IV) only

a. [Pt(NH 3)Cl 3] b. [PtCl2(NH 3) ]2 56. Consider that d 6 metal ion (M 2+) forms a complex with
c. [Ni(CO) 4] d. [Co(NO 2) (NH
3 )3 ]3 aqua ligands, and the spin only magnetic moment of the
complex is 4.90 BM. The geometry and the crystal field
50. Correct order of magnetic moment (spin only) for the
stabilization energy of the complex is :
following complexes [JEE Main P-I 2020]
[JEE Main P-II 2020]
(a) [Pd(PPh 3) 2]Cl 2 (b ) [Ni(CO) 4]
a. tetrahedral and –1.6t+1P b. octahedral and –2.40+2P
(c) [Ni(CN)4] 2 (d) [Ni(H 2O) 6] 2
c. tetrahedral and –0.6t d. octahedral and –1.60
438 JEE-Main and Advanced Chapter-wise Solved Papers: Chemistry
57. The one that is not expected to show isomerism is: 65. The molecule in which hybrid MOs involve only one d-
[JEE Main P-II 2020] robital of the central atom is: [JEE Main P-II 2020]
a. [Ni(NH 3) Cl
2 ]2 b. [Ni(NH 3) 4(H O)
2 ]2 2 a. [Ni(CN)4]2– b. XeF4
c. [CrF6]3– d. BrF5
c. [Ni3(en) 3] 2 d. [pt(NH 3) Cl
2 ]2
66. The one that can exhibit highest paramagnetic behaviour
58. The shape/structure of [XeF5 ] and XeO3F2 respectively among the following is: gly = glycinato ; bpy = 2, 2’-
are: [JEE Main P-II 2020] bipyridine [JEE Main P-II 2020]
a. Octahedral and square pyramidal a. [Fe(en)(bpy)(NH3)2]2+
b. Trigonal bipyramidal and trigonal bipyramidal b. [Pd(gly)2]
c. Triangular bipyramidal and pentagonal c. [Ti(NH3)6]3+
d. pentagonal planar and trigonal bipyramidal d. [Co(OX)2(OH)2]– (0>P)
59. The electronic spectrum of [Ti(H2O)6]3+ shows a single 67. The Crystal Field Stabilization Energy (CFSE) of
broad peak with a maximum at 20,300 cm –1. The crystal [CoF3(H2O)3] (0 < P) is: [JEE Main P-II 2020]
field stabilization energy (CFSE) of the complex ion, in kJ a. – 0.40 b. – 0.8 0
mol–1, is : (1 kJ mol–1 = 83.7 cm–1) [JEE Main P-II 2020] c. – 0.4 0 + P d. – 0.8 0 +2P
a. 242.5 b. 145.5
68. The pair in which both the species have the same
c. 83.7 d. 97
magnetic moment (spin only) is: [JEE Main P-II 2020]
60. The complex that can show optical activity is : a. [Cr(H2O)6]2+ and [Fe(H2O)6]2+
[JEE Main P-II 2020] b. [Co(OH)4]2– and [Fe(NH3)6]2+
a. trans-[Cr(Cl2)(ox)2]3– c. [Cr(H2O)6]2+ and [CoCl4]2–
b. trans-[Fe(NH3)2(CN)4]– d. [Cr(H2O)6]2+ and [Cr (H2O)6]2+
c. cis-[Fe(NH3)2(CN)4]–
69. The value of the crystal field stabilization energies for a
d. cis-[CrCl2(ox)2]3– (ox = oxalate)
high spin d 6 metal ion in octahedral and tetrahedral fields,
61. The d-electron configuration of [Ru(en) 3]Cl2 and respectively, are: [JEE Main P-II 2020]
[Fe(H2O)6]Cl2, respectively are: [JEE Main P-II 2020] a. 2.4 0 and  0.6  t b. 1.6 0 and  0.4  t
a. t 62g eg0 and t 42g eg2 b. t 42g eg2 and t 42g eg2
c. 0.4 0 and  0.27  t d. 0.4 0 and  0.6  t
6 0 6 0 4 2 6 0
c. t e and t e
2g g 2g g d. t e and t e
2g g 2g g
70. The species that has a spin-only magnetic moment of 5.9
62. Complex A has a composition of H 12O6Cl3Cr. If the BM, is: (Td  tetrahedral) [JEE Main P-II 2020]
complex on treatment with conc. H2SO4 loses 13.5% of a. Ni(CO) 4(T d) b. [Ni(CN)4 ]2(square planar)
its original mass, the correct molecular formulas of A is: 
c. [NiCl 4] 2(T )d d. [MnBr4] 2(T d)
[Given : atomic mass of Cr = 52 amu and Cl = 35 amu]
[JEE Main P-II 2020] 71. For a d 4 metal ion in an octahedral field, the correct
a. [Cr(H 2O 6]Cl 3 b. [Cr(H 2O) 4Cl ]Cl
2  O2
2H electronic configuration is: [JEE Main P-II 2020]
 O2
c. [Cr(H 2O) 3Cl ]3 3H  O
d. [Cr(H 2O) 5Cl]Cl 2 H 2
a. t 42g eg0 when o  P b. t 32g eg1 when o  P

63. The number of isomers possible for [Pt(en)(NO 2)2] is : c. t 32g eg1 when o  P d. e2g t 22g when o  P
[JEE Main P-II 2020]
72. Choose the correct statement(s) among the following :
a. 1 b. 2
[JEE Adv. 2020 P-I]
c. 3 d. 4
a. [FeCl4]  has tetrahedral geometry.
64. The pair in which both the species have the same
b. [Co(en)(NH3)2Cl2]+ has 2 geometrical isomers.
magnetic moment (spin only) is: [JEE Main P-II 2020] 
c. [FeCl4 ] has higher spin-only magnetic moment than
a. [Cr(H2O)6]2+ and [Fe(H2O)6]2+
b. [Co(OH)4]2– and [Fe(NH3)6]2+ [Co(en)(NH3)2Cl2]+.
c. [Cr(H2O)6]2+ and [CoCl4]2– d. The cobalt ion in [Co(en)(NH 3)2Cl2]+ has sp3d2
d. [Cr(H2O)6]2+ and [Cr (H2O)6]2+ hybridization.
Coordination Compounds 439
73. With respect to hypochlorite, chlorate and perchlorate ions, 79. The IUPAC name for the following compound is:
choose the correct statement(s). [JEE Adv. 2020 P-I] CHO
a. The hypochlorite ion is the strongest conjugate base. CH3
b. The hypochlorite ion is the strongest conjugate base. H3C
COOH
c. The hypochlorite and chlorate ions disproportionate to
[JEE Main P-II 2020]
give rise to identical set of ions.
a. 2, 5-dimethyl-6-carboxy-hex-3-enal
d. The hypochlorite ion oxidizes the sulfite ion.
b. 2, 5-dimethyl-5-carboxy-hex-3-enal
74. In an experiment, m grams of a compound X (gas / liquid / c. 6-formyl-2-methyl-hex-3-enoic
solid) taken in a container is loaded in a balance as shown d. 2, 5-dimethyl-6-oxo-hex-3-enoic acid
in figure I below. In the presence of a magnetic field, the
80. The calculated magnetic moments (spin only value) for
pan with X is either deflected upwards (fig. II), or deflected
downwards (fig. III), depending on the compound X. species [FeCl4] 2,[Co(C O
2 )4 ]3
3
and MnO 24 respectively
Identify the correct statement(s) [JEE Adv. 2020 P-II] are: [JEE Main P-I 2021]
(I) (II) (III) a. 5.92, 4.90 and 0 BM b. 5.82, 0 and 0 BM
Balanced ; Upward deflection ; Downward deflection ;
Magnetic field absent Magnetic field present Magnetic field present c. 4.90, 0 and 1.73 BM d. 4.90, 0 and 2.83 BM

81. The correct shape and I-I-I bond angles respectively in I 3

ion are: [JEE Main P-I 2021]
m X N N
S S a. Trigonal planar; 120°
b. Linear; 180º
magnet
c. Distorted trigonal planar; 135° and 90°
a. If X is H2O(l), deflection of the pan is upwards.
d. T-shaped; 180º and 90º
b. If X is K4[Fe(CN)6](s), deflection of the pan is upwards.
c. If X is O2(g), deflection of the pan is downwards. 82. The type of hybridisation and magnetic property of the
d. If X is C6H6(l), deflection of the pan is downwards. complex [MnCl6] 3, respectively, are :
75. T he IUPAC name of [Ni(NH3)4][NiCl4] is [JEE Main P-II 2021]
[JEE 2008 P-II] a. sp3 d 2 and diamagnetic b. d 2 sp3 and diamagnetic
a. Tetrachloronickel (II) – tetraamminenickel (II)
c. d 2 sp3 and paramagnetic d. sp3 d 2 and paramagnetic
b. Tetraamminenickel (II) – tetrachloronickel (II)
c. Tetraamminenickel (II) – tetrachloronickelate (II) 83. T he number of geometrical isomers found in the metal
d. Tetrachloronickel (II) – tetraamminenickelate (II) complexes [PtCl 2 (NH 3) 2], [Ni(CO) ],
4 [Ru(H O)
2 Cl
3 ]3


76. As per IUPAC nomenclature, the name of the complex and [CoCl 2(NH )3 4] respectively, are :
[Co(H 2O) 4(NH )3 ]Cl
2 3 is. [JEE 2012 P-I] [JEE Main P-II 2021]
a. Tetraaquadiaminecobalt (III) chloride a. 1, 1, 1, 1 b. 2, 1, 2, 2
b. Tetraaquadiaminecobalt (III) chloride c. 2, 0, 2, 2 d. 2, 1, 2, 1
c. Diaminetetraaquacobalt (III) chloride
84. The calculated spin only magnetic moments of
d. Diamminetetraaquacobalt (III) chloride 3 3
[Cr(NH 3) ]6 and [CuF6 ] in BM, respectively, are
77. The total number of isomers for a square planar complex
(Atomic numbers of Cr and Cu are 24 and 29,
[M(F)(Cl)(SCN)(NO2)] is : [JEE Main 2019]
respectively) [JEE Adv. 2021 P-I]
a. 12 b. 8
a. 3.87 and 2.84 b. 4.90 and 1.73
c. 16 d. 4
c. 3.87 and 1.73 d. 4.90 and 2.84
3
78. For the complex [Ma 2b 2] if M is sp or dsp 2 hybridised
85. The pair(s) of complexes wherein both exhibit tetrahedral
respectively then total number of optical isomers are geometry is(are) (Note: py  pyridine
respectively: [JEE Main P-I 2020] Given: Atomic numbers of Fe, Co, Ni and Cu are 26, 27,
a. 1, 1 b. 2, 1 28 and 29, respectively) [JEE Adv. 2021 P-II]
c. 0, 0 d. 1, 2
440 JEE-Main and Advanced Chapter-wise Solved Papers: Chemistry

a. [FeCl4] and [Fe(CO) 4] 2 92. Which of the following pair of molecules contain odd
electron molecule and an expanded octet molecule?
b. [Co(CO) 4]  and [CoCl 4] 2
[JEE Main P-II 2022]
c. [Ni(CO) 4] and [Ni(CN) 4] 2 a. BCl3 and SF6 b. NO and H2SO4
d. [Cu(py) 4]  and [Cu(CN) 4] 3 c. SF6 and H2SO4 d. BCl3 and NO

86. Identify the correct statement for B 2H6 from those given Matrix Match/Column Match
below. 93. Match the complexes in Column I with their properties
(a) In B 2H6, all B-H bonds are equivalent. listed in Column II. [JEE 2007 P-I]
(b) In B 2H6 there are four 3-centre-2-electron bonds. Column I Column II
(c) B 2H6 is a Lewis acid. (A) [Co(NH 3) (H O) 1. geometrical isomers
4 2 ]Cl
2 2
(d) B 2H6 can be synthesized form both BF3 and NaBH4.
(B) [Pt(NH 3) Cl
2 ]2
2. paramagnetic
(e) B2H6 is a planar molecule.
Choose the most appropriate answer from the options (C) [Co(H 2O) 5Cl]Cl 3. diamagnetic
given below: [JEE Main P-I 2022] (D) [Ni(H 2O) 6]Cl 2 4. metal ion with +2
a. (a) and (e) only b. (b), (c) and (e) only oxidation state
c. (c) and (d) only d. (c) and (e) only a. A→ 1,2,4; B→ 1,3,4; C→ 2,4; D→ 2,4
87. Transition metal complex with highest value of crystal b. A→ 1,3,4; B→ 1,2,4; C→ 2,4; D→ 2,3
c. A→ 1,2,4; B→ 1,2,3; C→ 2,3; D→ 1,2
field splitting (  0 ) will be [JEE Main P-I 2022]
d. A→ 1,2,4; B→ 1,3,4; C→ 1,2,3,4; D→ 2
a. [Cr(H 2O) 6] 3+ b. [Mo(H 2O) 6] 3+
94. Match each coordination compound in Column-I with an
c. [Fe(H 2O) 6] 3+ d. [Os(H 2O) 6] 3+ appropriate pair of characteristics from Column-II.
88. Octahedral complexes of copper (II) undergo structural {en  H 2NCH CH
2 NH
2 ;2 Atomic numbers : Ti  22, Cr 
distortion (Jahn-Teller). Which one of the given copper 24, Co  27, Pt  78} [JEE Adv. 2014 P-II]
(II) complexes will show the maximum structural Column I Column II
distortion ? [JEE Main P-II 2022] (A) [Cr(NH 3 ) 4 Cl 2 ]Cl 1. Paramagnetic and
(en–ethylenediamine; H 2 N CH 2 CH 2 NH 2) exhibits ionization
a. [Cu(H 2O) 6]SO b. [Cu(en)(H 2O) ]SO isomerism
4 4 4
(B) [Ti(H 2 O)5 Cl](NO3 )2 2. Diamagnetic and
c. cis-[Cu(en) 2Cl ]2 d. trans-[Cu(en) 2Cl ]2
exhibits cis-trans
89. The correct order of energy of absorption for the isomerism
following metal complexes is [JEE Main P-II 2022] (C) [Pt(en)(NH 3)Cl]NO 3 3. Paramagnetic and
2+ 2+
A: [Ni(en)3] , B: [Ni(NH 3) 6] , C: [Ni(H 2O) 6] 2+ exhibits cis-trans
a. C < B < A b. B < C < A isomerism
c. C < A < B d. A < C < B (D) [Co(NH3) 4(NO3) 2 ]NO3 4. Diamagnetic and
exhibits ionization
90. The IUPAC nomenclature of an element with electronic isomerism
configuration [Rn]5f 14 6d 17s 2 is : [JEE Main P-II 2022] a. A→1; B→3; C→4; D→2
a. Unnilbium b. Unnilunium b. A→3; B→1; C→4; D→2
c. Unnilquadium d. Unniltrium c. A→1; B→2; C→ 3; D→4
d. A→2; B→3; C→4; D→1
91. The geometry around boron in the product 'B' formed
from the following reaction is
450 K
95. Match column I with Column II. [JEE Main P-I 2022]
BF3 + NaH  A + NaF
Column I Column II
B
A + NMe 3  [JEE Main P-II 2022] (A) [PtCl ]2 1. sp3d
4
a. trigonal planar b. tetrahedral 2. d2sp3
(B) BrF5
c. pyramidal d. square planar
Coordination Compounds 441
2
(C) PCl5 3. dsp Paragraph
3 2
4. sp d Paragraph for Question No. 99 to 101
(D) [Co(NH 3 ) 6] 3
The coordination number of Ni 2 is 4 [JEE 2006]
a. A→ 2; B→ 4; C→ 1; D→3 NiCl 2  KCN (excess)   A (cyano complex)
b. A→ 3; B→ 4; C→ 1; D→ 2
B (chloro complex)
NiCl 2  Conc.HCl (excess) 
c. A→ 3; B→ 1; C→ 4; D→ 2
d. A→ 2; B→ 1; C→ 4; D→ 3 99. The IUPAC name of A and B are
a. Potassium tetracyanonickelate (II), potassium tetra-
96. Column I contains metal species and column II contains chloronickelate (II)
their properties. [Given: Atomic number of Cr  24, Ru  b. Tetracyanopotassiumnickelate (II), teterachlorpotassi-
44, Fe = 26] Metal each metal species in Column with umnickelate (II)
their properties in Column II, and choose the correct c. Tetracyanornickel (II), tetrachloronickel (II)
option. [JEE Adv. P-I 2022] d. Potassium tetracyanonickel (II), potassium tetra-
Column I Column II chloronickel (II)
(A) [Cr(CN) 6] 4 1. t2g orbitals contain 4 electrons
100. Predict the magnetic nature of A and B.
2
(B) [RuCl6] 2.  (spin-only) 4.9 BM a. Both are diamagnetic
2 3. low spin complex ion b. A is diamagnetic and B is paramagnetic with one
(C) [Cr(H 2O) 6]
unpaired electron.
2
(D) [Fr(H 2O) 6] 4. metal ion in 4  oxidation state c. A is diamagnetic and B is paramagnetic with two
5. d4 species unpaired electrons
a. A  3,5; B  1,4; C  2,5; D  1, 2 d. Both are paramagnetic
b. A ; B  1,5; C  1,3; D  2,5 101. The hybridization of A and B are
c. A  1,3; B  3,4; C  3,5; D  1,5 a. dsp2, sp3 b. sp3, sp3
d. A  2,5; B  4,5; C  1,5; D  2,3 c. dsp 2 ,dsp 2 d. sp3d 2, d 2sp 3

Statement/Assertion and Reason Paragraph for Question No. 102 and 103
97. Statement-I: [Fe(H 2O) 5 NO]SO 4 is paramagnetic. And An aqueous solution of metal ion M1 reacts separately with
reagents Q and R in excess to give tetrahedral and square planar
Statement-II: The Fe in [Fe(H 2O) 5 NO]SO 4 has three
complexes, respectively. An aqueous solution of another metal
unpaired electrons. [JEE 2008 P-II] ion M2 always form tetrahedral complexes with these reagents.
a. Statement-I: is True, Statement-II is True; Statement-II: Aqueous solution of M2 on reaction with reagent S gives white
is correct explanation for Statement-I precipitate which dissolves in excess of S. The reactions are
b. statement-I is True, Statement-II: is True; statement-II summarized in the scheme given below. [JEE Adv. 2014 P-II]
is not a correct explanation for statement-I Scheme:
c. statement-I is True, statement-II is False Q R
Tetrahedral 
excess
M1 
excess
 Square planar
d. statement-I is False, statement-II is True
Q R
Tetrahedral 
excess
M2 
excess
 Tetrahedral
98. Given below are two statements: [JEE Main P-II 2021]
S,
S, stoichiometric amount
stoichiometricamount
Statement I : [Mn(CN)6 ]3 ,[Fe(CN)6] 3 and [Co(C2O 4) ]3 3

are d2sp3 hybridized. White


S Precipitate
Precipitate excess dissolves
3 3
Statement II : [MnCl 6] and [FeF6 ] are paramagnetic
and have 4 and 5 unpaired electrons, respectively. 102. M1, Q and R, respectively are
In the light of the above statements, choose the correct a. Zn 2+, KCN and HCl b. Ni 2+ , HCl and KCN
answer from the options given below : c. Cd 2+ , KCN and HCl d. Co 2+ , HCl and KCN
a. Statement I is correct but statement II is false
103. Reagent S is
b. Both statement I and statement II are false
a. K 4 [Fe(CN) 6 ] b. Na 2 HPO 4
c. Statement I is incorrect but statement II is true
d. Both statement I and statement II are are true c. K 2 CrO 4 d. KOH
442 JEE-Main and Advanced Chapter-wise Solved Papers: Chemistry
Integer and Subjective Assume that both the reactions are 100% complete. If
104. Total number of geometrical isomers for the complex 1584 g of ammonium sulphate and 952 g of NiCl 2.6H O
2

[RhCl(CO)(PPh 3)(NH 3)] is________ [JEE 2010 P-II] are used in the preparation, the combined weight (in
grams) of gypsum and the nickel-ammonia coordination
105. EDTA 4  is ethylenediaminetetra acetate ion. The total compound thus produced is_____. (Atomic weights in g
number of N – Co – O bond angles in [Co(EDTA)]1– mol–1 : H  1, N  14, O  16, S  32, Cl  35.5, Ca  40,
complex ion is ________ Ni  59) [JEE Adv. 2018 P-I]
[JEE Adv. 2013 P-I]
113. The oxidation states of iron atoms in compounds (A), (B)
106. If the freezing point of a 0.01 molal aqueous solution of a and (C), respectively, are x, y and z. The sum of x, y and z
cobalt (III) chloride-ammonia complex (which behaves as is _____
a strong electrolyte) is 0.0558C, the number of Na 4 [Fe(CN) 5(NOS)] Na 4 [FeO 4] [Fe2(CO) 9]
(A) (B) (C)
chloride(s) in the coordination sphere of the complex is
[JEE Main P-II 2020]
[ K f of water = 1.86 K kg mol–1] [JEE Adv. 2015 P-I]
114. Considering that  0  P, the magnetic moment (in BM) of
107. For the octahedral complexes of Fe3 in 2
[Ru(H 2O) 6] would be .................[JEE Main P-II 2020]
SCN  (thiocyanato-S) and in CN  ligand environments,
the difference between the spin-only magnetic moments in 115. The atomic number of Unnilunium is______
Bohr magnetons (When approximated to the nearest [JEE Main P-II 2020]
integer) is [Atomic number of Fe = 26] ________
116. An acidified solution of potassium chromate was layered
[JEE Adv. 2015 P-I]
with an equal volume of amyl alcohol. When it was
108. In the complex acetylbromidodicarbonylbis (triethyl- shaken after the addition of 1 mL of 3% H2O2, a blue
phosphine)iron(II), the number of Fe–C bond(s) is______ alcohol layer was obtained. The blue color is due to the
[JEE Adv. 2015 P-II] formation of a chromium (VI) compound 'X' . What is the
number of oxygen atoms bonded to chromium through
109. Among the complex ions,
only single bonds in a molecule of X?
[Co(NH 2 CH 2 CH 2 NH 2) 2
[JEE Adv. 2020 P-II]
Cl2 ], [CrCl2(C 2O 4) ]2 3, [Fe(H2O)4(OH)2] , [Co(NH 2 
117. 3 moles of metal complex with formula Co(en) 2Cl3 gives 3
CH 2  CH 2  NH 2 )2 (NH 3 )Cl] 2  [Fe(NH 3) (CN)
2 ]4 ,  and moles of silver chloride on treatment with excess of silver
2
[Co(NH 3) (H
4 O)Cl]
2 , the number of complex ion(s) that nitrate. The secondary valency of Co in the complex is
show(s) cis-trans isomerism is________ _____. (Round off to the nearest integer)
[JEE Adv. 2015 P-II] [JEE Main P-II 2021]

110. The number of geometric isomers for the complex 118. The maximum number of possible isomers (including
 stereoisomers) which may be formed on mono-
[CoL2Cl 2] (L H NCH
2 2 CH 2 O  ) is________
bromination of 1-methylcyclohex-1-ene using Br 2 and UV
[JEE Adv. 2016 P-I]
light is ____ [JEE Adv. 2021 P-I]
111. Among the species given below, the total number of
119. In the cobalt-carbonyl complex: [Co2(CO)8], number of
diamagnetic species is ____. H atom, NO2 monomer, O 2 Co-Co bonds is "X" and terminal CO ligands is "Y". X +
(superoxide), dimeric sulphur in vapour phase, Mn 3O 4 , Y ____ [JEE Main P-I 2022]
(NH 4 )2[FeCl 4 ], (NH 4 ) 2[NiCl 4],K MnO 4, K 2 CrO 4
2 120. Sum of oxidation state (magnitude) and coordination
[JEE Adv. 2018 P-I] number of cobalt in Na[Co(bpy)Cl 4] is_________.
112. The ammonia prepared by treating ammonium sulphate [Given bpy  ]
with calcium hydroxide is completely used by N N
NiCl 2.6H O
2 to form a stable coordination compound. [JEE Main P-II 2022]
Coordination Compounds 443
121. [Fe(CN)6] 3– should be an inner orbital complex. Ignoring
the pairing energy, the value of crystalfield stabilization
energy for this complex is (–) _________ o. (Nearest
integer) [JEE Main P-II 2022]

122. The number of geometrical isomers possible in

triamminetrinitrocobalt (III) is X and in
trioxalatochromate (III) is Y. Then the value of X + Y is
_______. [JEE Main P-II 2021]

123. Consider the following metal complexes:

[Co(NH 3)] 3+
2+
[CoCl(NH3) 5]
[Co(CN) 6] 3
3+
[Co(NH 3) 5(H O)]
2

T he spin-only magnetic moment value of the complex that

absorbs light with shortest wavelength is B.M. (Nearest
integer) [JEE Main P-II 2022]