Chapter 18

Co-ordination Compounds
1. Answer (D)
2. Answer (B)
[Ni(CO)4] --------- sp3 hybridization
[Ni(CN)4]–2 --------- dsp2 hybridization
3. Answer (A)
Cr(CO)6

Cr in G.S.
Under the influence
of strong ligand

2 3
d sp hybridization

Diamagnetic  = 0
4. Answer (B)
Cr(H2O)4Cl(NO2)]Cl and [Cr(H2O)4Cl2](NO2) have same molecular formula but they give different ions on
ionization.
5. Answer (C)

HOOC CH2 CH2 COOH

N CH2 CH2 N
HOOC CH2 CH2 COOH

6. Answer (B)
Ni2+ is sp3 hybridized and metal ion is connected with weak ligands.
 Ni2+  d 8

two unpaired electrons sp3

 s = 2 (2  2) B.M.

= 8 B.M. = 2.83 B.M.

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7. Answer (B)
Ni+2 + 4Cl–  [NiCl4]–2 (tetrahedral)
Ni+2 + 4CN–  Ni(CN)4–2 (square planar)
Ni+2 + H2O  Ni(H2O)6+2 (octahedral)
8. Answer (C)
[Co(NH3)6]Cl3 d 2sp3 diamagnetic
Na3[Co(OX)3] d 2sp3 diamagnetic
K2[Pt(CN)4] dsp2 diamagnetic
[Zn(H2O)6](NO3)2 sp3d2 diamagnetic
9. Answer (D)
10. Answer (C)
The hybridisation of Ni2+ in paramagnetic complex is sp3 and hence the complex is tetrahedral. The diamagnetic
complex is square planar as the hybridisation of Ni2+ is dsp2.
11. Answer (B)
The electronic configuration of central metal ion in complex ions P, Q and R are

P  [FeF6 ]3  ; Fe3  :
3d

Q = [V(H2O)6]2+; V2+:
3d

R = [Fe(H2O)6]2+; Fe2+
3d

The correct order of spin only magnetic moment is Q < R < P

12. Answer (B)
[NiCl4]2– and Na3[CoF6] are paramagnetic since involve weak field ligand. CsO2 is paramagnetic due to
paramagnetism by O2–.
13. Answer (A)

2
Ni2   6NH3  Ni  NH3 6 
octahedral
2
Pt 2   4NH3  Pt NH3 4 
(square planar )

2
Zn2   4NH3   Zn NH3 4 
tetrahedral

14. Answer (A)

[Cr(NH3)6]3+ = Cr3+
Cr3+ = 3d3 4s0
It has 3 unpaired electrons

  n(n  2) BM

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 3(3  2) BM
= 3.87 BM
[CuF6]3– = Cu+3
Cu+3 = 3d8 4s0
It has 2 unpaired electrons

  2(2  2) BM

= 2.84 BM
15. Answer (C, D)

Cl
en
Cl

(C) en Pt en &

Cl
en
Cl

Cl NH3 Cl NH3

(D) Pt & Pt

NH3 Cl Cl NH3

16. Answer (B, D)

The pair of complex ions [Co(NH3)4Cl2]+ and [Pt(NH3)2(H2O)Cl]+ show geometrical isomerism. The pair of
complexes [Pt(NH3)3(NO3)]Cl and [Pt(NH3)3Cl]Br show ionisation isomerism. The other pairs given do not have
same type of isomerism.
17. Answer (A, B, C)
(X) = CoCl26H2O, or, [Co(H2O)6]Cl2 (Pink)
Co2+ = [Ar]
3d
H2O is weak field ligand, therefore No pairing of electron
 Number of unpaired electron, n = 3

 s  n(n  2) B.M.

= 15 B.M.
= 3.87 B.M.



[Co(H2O)6 ]2   6NH3(aq)  2
 [Co(NH3 )6 ]  6H2O

O2 will oxidise [Co(NH3)6]2+ to [Co(NH3)6]3+, therefore shift in forward.

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 Y = [Co(NH3)6]3+Cl3 [1 : 3 complex]

Co(III) = [Ar]
3d

NH3 is strong field ligand

 Forces electrons to pair up.
 n=0
 = 0 B.M.

[Co(NH3)6]3+ = [Ar]
3d 4s 4p
d2sp3

+ 6H2O; H = +ve
2+ – 2–
Also, [Co(H2O)6] + 4Cl [CoCl4] (aq)

(X) (Z)
(Pink) Blue

At 0°C, equilibrium shifts in backward, therefore pink colour.

18. Answer (B, C)
(A) Valence shell electrons in iron in compound Fe(CO)5.
Fe(26) – 1s2, 2s2, 2p6, 3s2, 3p6, 3d8 (after pairing of electrons)

3d 4s 4p
3
dsp Hybridization

Valence = 2 + 6 + 8 = 16
Electrons (3rd shell)
Valence shell electrons in nickel in compound Ni(CO)4
Ni(28) - 1s2, 2s2, 3s2, 3p6 ,3d10

3d
3
sp Hybridization

Valence electrons (3rd shell) = 2 + 6 + 10 = 18

(B) Both complexes are formed in low spin condition due to strong field ligand 'CO'.
(C) Metal carbon bond strengthens when complex is formed in lower oxidation number of metal. Since in lower
oxidation number; number of electrons in d-subshell are higher, so it can donate more electrons in ABMO
of ligands and increases the double bond character between metal and carbon.
(D) In higher oxidation number, metal may have less number of electrons in d-orbitals, which decreases the
extent of synergic bonding.

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19. Answer (A, B, D)

(A) [Co(en)(NH3)3(H2O)]3+

3+ 3+
OH2 NH3

CH 2 H2N NH 3 CH 2 NH2 OH2

Co Co

CH 2 NH2 NH 3 CH 2 NH2 NH 3

NH3 NH3

(B) [Co(CN)2(NH3)3(H2O)]1+

1+ 1+ 1+
OH2 NH3 CN

NC NH3 NC OH2 H3N OH 2

Co Co Co
NC NH3 NC NH3 H 3N NH3

NH3 NH3 CN

(C) Co3+ = [Ar]3d6

in presence of en and NH3 it form low spin complex.
(D) [Co(en)(NH3)4]3+ has larger gap between eg and t2g than [Co(en)(NH3)3(H2O)]3+. So [Co(en)(NH3)3(H2O)3+
absorb longer wavelength than [Co(en)(NH3)4]3+.
20. Answer (A, C)
[FeCl4]–

+3 5
Fe = 3d
x x x x
x x x x

Cl Cl Cl Cl
3
sp hybridization
tetrahedral

[Co(en)(NH3)2Cl2]+ has 3 geometrical isomers, one of them is optically active. So, it has 4 stereoisomers.

Cl Cl en en
NH3 H 3N Cl H3N
en Co Co en Co Co
Cl Cl H3N Cl Cl NH 3
NH3 NH3 NH3 Cl
(I) (II) (III) (IV)

I and II are enantiomers.

Co+3 = 3d6
d2sp3 hybridization

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21. Answer (A, B, D)

[FeCl4]–  Fe3+, 3d5 (weak field ligand) = sp3
[Fe(CO)4]–2  Fe2–, 3d10  sp3
[Co(CO)4]–  Co–, 3d10  sp3
[CoCl4]2–  Co2+, 3d7 (weak field ligand)  sp3
[Ni(CO)4]  Ni, 3d10  sp3
[Ni(CN)4]2–  Ni2+, 3d8 (strong field ligand)  dsp2
[Cu(py)4]+  Cu+, 3d10  sp3
[Cu(CN)4]3–  Cu+, 3d10  sp3
In 3d10 electronic configuration only sp3 hybridisation and tetrahedral geometry is possible.
22. Answer (B)
23. Answer (A)
24. Answer (C)
Solution of Q. Nos. 22 to 24

Cu  Ag  Cu 2  Ag

Ag  NaCl  AgCl

White ppt

AgCl  NH3 [Ag(NH3 )2 ] Cl

Cu2  NH3  Cu(NH3 )24

(Blue)

M - Cu
N - Solution of AgNO3
O - AgCl
25. Answer (B)
Ni+2 + HCl  [NiCl4]–2
Ni+2 + KCN  [Ni(CN)4]–2
26. Answer (D)

Zn2   OH  Zn(OH)2 
OH
 [Zn(OH)4 ]2 
white ppt Soluble
27. Answer A(p, q, s); B(p, r, s); C(q, s); D(q, s)
28. Answer (B)
Hint : Magnetic character Isomerism
P. [Cr(NH3)4Cl2]Cl Paramagnetic cis/trans
Q. [Ti(H2O)5Cl](NO3)2 Paramagnetic ionization
R. [Pt(en)(NH3)Cl]NO3 Diamagnetic ionization
S. [Co(NH3)4(NO3)2]NO3 Diamagnetic cis/trans

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29. Answer (C)

1. [FeF6]4–
3d 4s 4p
Fe+2
High spin complex because F– is weak field ligand.
sp3d2
2. [Ti(H2O)3Cl3]

Ti3+ d2 sp3

d2 sp3
3. [Cr(NH3)6]3+
2 3
Cr3+ d sp

d 2sp3
4. [FeCl4]2–
Fe+2 : 3d6, Cl– is weak field ligand.
3d 4s 4p

sp 3
5. Ni(CO)4
Ni0 – 3d84s2, CO is strong field ligand

Ni

sp 3

6. [Ni(CN)4]2–

Ni +2
dsp2

CN– is strong field ligand.

30. Answer (A)

(I) [Cr(CN)6]4–

Cr+2 = [Ar] 3d4 4s0

It is d2sp3 hybridised as CN– is a strong field ligand.

(II) [RuCl6]2–

Ru+4 = [Kr] 4d4 5s0

t2g set contains 4 electron.

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(III) [Cr(H2O)6]2+

Cr+2 = [Ar] 3d4 4s0

It has 4 unpaired e– as H2O is weak field ligand.

So, its  = 4.9 B.M.

(IV) [Fe(H2O)6]2+

Fe2+ = [Ar]3d6 4s0

= t2g4 e2g

It has 4 unpaired e–, its  = 4.9 B.M.

31. Answer (3)
Rh Cl(CO)(PPh3)(NH3)] is a square planar complex with four different ligands and hence it will have three
geometrical isomers
a b a b a c

Rh Rh Rh

d c c d d b
32. Answer (6)
Applying equation,
N1V1 = N2V2
0.1 × V = 2 × 0.01 × 30
2  30  10
V 6
100  1
33. Answer (8)
I
O O–C=O
C CH2 CH2
I
II O N
CH2
Co
II CH2
III O N
C CH2
CH2
O O–C=O
IV
So, bond angles are
(1) NI CoOI
(2) NI CoOII
(3) NI CoOIII
(4) NI CoOIV
(5) NII CoOI
(6) NII CoOII
(7) NII CoOIII
(8) NII CoOIV
So, total asked bond angles are 8.
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34. Answer (4)

F F
F
F F F
Xe S Si B
F F F F F F F
F F
F 2–
Cl
F F NH3 NH3
Br Cu Fe
F F NH3 NH3 Cl Cl
Cl
2–
Cl 2–
Cl Cl
Co Pt
Cl Cl Cl Cl
Cl

35. Answer (1)

Given Tf = 0.0558°C
as we know, Tf = i × Kf × m
 0.0558 = i × 1.86 × 0.01

 i3

Therefore, the complex will be [Co(NH3)5Cl]Cl2.

Hence, number of chloride in co-ordination sphere is 1.
36. Answer (4)
Fe(26)  [Ar]18 3d64s2
Fe3+  [Ar]18 3d54s0
SCN– is weak field ligand hence pairing will not occur.
3+
 Fe
Unpaired electrons = 5

Magnetic moment  5(5  2) B.M.  35 B.M.  5.92 B.M.

CN– is strong field ligand hence pairing will take place.

3+
 Fe

Unpaired electrons = 1

Magnetic moment  1(1  2) B.M.  3 B.M.  1.732

Difference = 5.92 – 1.732 = 4.188

Hence answer is (4).

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37. Answer (3)

Et3P CO
O
– +2 –
CH3 – C Fe Br

Et3P CO

38. Answer (6)

Cl N
N N N Cl
Co Co
N N N Cl
Cl N

Cl O
O O O Cl
Cr Cr
O O O Cl
Cl O

NH3 NH3
NC CN NC NH3
Fe Fe
NC CN NC CN
NH3 CN

NH3 NH3
NH2 NH2 NH2 Cl
Co Co
NH2 NH2 NH2 NH2
Cl NH2

OH2 OH2
H3N NH3 H3N Cl
Co Co
H3N NH3 H3N NH3
Cl NH3

H2O OH
H2O OH H2O OH2
Fe Fe
H2O OH H2O OH2
H2O OH

(All the six complexes will show cis-trans isomerism)

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39. Answer (5)

– –
Cl Cl
O O NH2 O
Co Co
NH2 NH2 O NH2
Cl Cl

– –
O NH2
NH2 Cl O Cl
Co Co
NH2 Cl O Cl
O NH2

–
O
H2N Cl
Co
O Cl
NH2

40. Answer (1)

H atom :

NO2 Monomer :

2p2x  * 2p2x
O2– (Superoxide) : 1s2, *1s2, 2s2, *2s2, 2pz2,
2p2y  * 2p1y

One unpaired electron is present in either *2px or *2py. So, it is paramagnetic in nature.
Dimeric sulphur in vapor phase : It is similar as O2 in vapor state, paramagnetic in nature.
Mn3O4 : It is combined form of MnO and Mn2O3
Mn+2 has 5 unpaired electrons (d5 electronic configuration)
Mn+3 has 4 unpaired electrons (d4 electronic configuration)
So, it is paramagnetic in nature.
(NH4)2[FeCl4] : Consist [Fe+2Cl4]–2 ion.
[FeCl4]–2 : Tetrahedral, sp3 Hybridized, has configuration eg3, t2g3. (Paramagnetic in nature)
(NH4)2[NiCl4] : Consist [Ni+2Cl4]–2 ion.
[NiCl4]–2 : Tetrahedral, sp3 Hybridized, has configuration eg4, t2g3. (Paramagnetic in nature)
K2MnO4 : Mn+6 is present in compound which has one unpaired electron in 3d subshell. Mn+6 - [Ar]3d1
Paramagnetic in nature.
K2CrO4 : Cr+6 is present in compound which has zero unpaired electron, diamagnetic in nature.

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41. Answer (2989 – 2995)

12(NH4)2SO4 + 12Ca(OH)2 + 4NiCl2  6H2O

12CaSO4  2H2O + 4[Ni(NH3)6]Cl2 + 24H2O

952
nNiCl 2  6H2O = = 4 mol
238

Mass = 12  MCaSO4 2H2O  4M[Ni(NH3 )6 ]Cl2

= (12 × 172) + (4 × 232) = 2992 g

42. Answer (6)
cis-[Mn(en)2Cl2]

Cl
H 2N
CH 2
Cl
CH 2
NH 2 Mn

NH 2
H 2N CH 2
CH 2

No. of N-Mn-Cl bonds (in which N-Mn bond is cis to Mn-Cl bonds) = 6
(Two N-Mn-Cl bonds have N-Mn bond trans to Mn-Cl bonds)
43. Answer (6)
The given complex [Pt(NH3)4Cl2]Br2 has three ionisation isomers and each of them has two geometrical isomers.
Cl Cl Cl Cl
H3N Cl H3N NH3 H3N Br H3N NH3

Pt Pt Pt Pt

H3N NH3 H3N NH3 H3N NH3 H3N NH3

NH3 Cl NH3 Br
(cis) (trans) (cis) (trans)

Br Br
H3N NH3 H3N Br

Pt Pt

H3N NH3 H3N NH3

Br NH3
(trans) (cis)


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