Inorganic Chemistry

1
Coordination Chemistry
2
1. Ni(CN4)2- and Ni(Cl4)2- complex ions are :

[CSIR-JUNE 2011]
(a) Both diamagnetic.
(b) Both paramagnetic
(c) Diamagnetic and paramagnetic respectively
(d) Antiferromagnetic and diamagnetic respectively
2. According To Crystal Field Theory, Ni2+ can two have unpaired electrons in
[CSIR-JUNE 2011]
(a) Octahedral geometry only
(b) Square planar geometry only
(c) Tetrahedral geometry only
(d) Both octahedral and tetrahedral geometry
3. The term symbol of a molecule with electronic configuration:

(1σg)2 (1σu)2 (2σg)2 (2σu)2 (1πu)1 (1πu)1 is: [CSIR-JUNE 2011]
(a) 1∑+g
(b) 3∑-g
(c) 1∑ - g
(d) 3∑ g+
4. Consider two redox pairs:

(1) Cr(II)/Ru(III)
(2) Cr(II)/Co(III)
The rate of acceleration in going from a outer-sphere to a inner-sphere mechanism is lower for (1)
relative to (2). Its correct explanation is [CSIR-JUNE 2011]
(a) HOMO/LUMO are ϭ* and ϭ* respectively.

(b) HOMO/LUMO are ϭ* and π* respectively.
(c) HOMO/LUMO are π* and ϭ*and respectively.
(d) HOMO/LUMO are π* and π*respectively.
5. The complex [Mn (H2O)6]+2has very light pink colour. The best reason for it is
[CSIR-JUNE 2011]
(a) the complex does not have a charge transfer transition.
(b) d-d transitions here are orbital forbidden but spin allowed.
(c) d-d transitions here are orbital allowed but spin forbidden.
(d) d-d transitions here are both orbital forbidden and spin forbidden.
6. The correct order of LMCT energies is: [CSIR-JUNE 2011]

(a)MnO4- < CrO42- < VO43-
(b) MnO4-> CrO42- > VO43-
(c)MnO4-> CrO42- < VO43-
(d)MnO4- < CrO42- > VO43-
7. For the complexes

3
(A) [Ni(H2O)6] +2
(B) [Mn(H2O) 6] +2
(C) [Cr(H2O) 6] +3
(D) [Ti(H2O) 6 ] +3
the ideal octahedral geometry will not be observed in [CSIR-JUNE 2011]
(a) (A) and (D)

(b) (C) and (D)
(c) (B) only
(d) (D) only
8. The possible J values for 3D term symbol are [CSIR-JUNE 2011]

(a) 2
(b) 3
(c) 4
(d) 5
9. Which of the following compound show a charge-transfer band? [CSIR-JUNE 2011]

(a) Lanthanum nitrate.
(b) Ceric ammonium nitrate
(c) Manganese (II) acetate
(d) Copper (II) sulphate pentahydrate
10. Cis and trans complexes of the type [PtA²X²] are distinguished by
[CSIR-JUNE 2011]
(a) Chromyl chloride test
(b) Carbylamine test
(c) Kurnakov test
(d) Ring test
11. The number of possible isomers for [Ru(bpy)2Cl2] is (bpy = 2,2‫׳‬- bipyridine)
[CSIR-JUNE 2011]
(a) 2
(b) 3
(c) 4
(d) 5
12. The term symbol for the ground state of nitrogen atoms is [CSIR-DEC 2011]
4
(a) 3P0
(b) 4P3/2
(c) 1P1
(d) 4S3/2
13. The complex that absorbs light of shortest wavelength is [CSIR-DEC 2011]
(a) [CoF6]3–
(b) [Co(H20)6]3+
(c) [Co(NH3) 6]3+
(d) [Co(ox)3]3- (ox=C2O42-)
14. Green coloured Ni(PPh2Et)2Br2 , has a magnetic moment of 3.20 B.M. The geometry and the
number of isomers possible for the complex respectively, are [CSIR-DEC 2011]
(a) Square planar and one
(b) Tetrahedral and one
(c) Square planar and two
(d) Tetrahedral and two
15. Observe the following electronic transition of a diatomic molecule.

(a) 1∑+g →3∑+g
(b) 1∑+u →1∑+g
(c) 1Δu → 1∑+g
(d) 1πg →1∑+u
The allowed transitions are [CSIR-DEC 2011]
(a) (A) and (C) only

(b) (B) and (D) only
(c) (A), (B) and (C) only
(d) (A). (C) and (D) only
16. The electronic spectrum of [CrF6] 3- shows three bands at 14, 900 cm-1 , 22400
cm-1 and 34, 800 cm-1. The value of Δo in this case is:
[CSIR-DEC 2011]
-1
(a) 5,500 cm
(b) 14,900 cm-1
(c) 22,400 cm-1
(d) 34,800 cm-1
17. A true statement about base hydrolysis of [Co(NH3)5Cl]+2 is: [CSIR-DEC 2011]
(a) It is a first order reaction
(b) The rate determining step involves the dissociation of chloride in [Co(NH3)4(NH2)Cl]+
(c) The rate is independent of the concentration of the base.
(d) The rate determining step involves the abstraction of a proton from [Co(NH3)5Cl]+2
5
18. The correct order of d-orbital splitting in a trigonal bipyramidal geometry is:
[CSIR-DEC 2011]
(a) dz² > dxz > d x2-y2, dxy
(b) dxz , dyz >d x2-y2, dxy > dz²
(c) d x2-y2, dxy > dz² > dxz , dyz
(d) dz² > d x2-y2> dxy > dxz , dyz
19. For the following outer sphere electron transfer reactions.

[CSIR-DEC 2011]
[Co(NH3) 6] +2 + [Co*(NH3) 6] +3 → [Co(NH3) 6] +3 + [Co*(NH3) 6] +2
[Ru(NH3) 6] +2 + [Ru*(NH3) 6] +3 → [Ru(NH3) 6] +3 + [Ru*(NH3) 6] +2
the rate constants are 10 M-1s-1 and 8.2x10 M-1s-1 respectively. This difference in the rate constants
is due to
(a) A change from high spin to low spin in Co* and high spin to low spin in Ru.
(b) A change from high spin to low spin in Co* and low spin to high spin Ru*.
(c) A change from low spin to high spin in Co* and the low spin state remains unchanged in Ru.
(d) A change from low spin to high spin in Co* and high spin to low spin in Ru*.
20.The coordination number and geometry of cerium in [Ce(NO3)6] -2 are respectively,

[CSIR-DEC 2011]
(a) 6 and octahedron
(b) 6 and trigonal prism
(c) 8 and cubic
(d) 12 and icosahedron
21. As a ligand Cl- is: [CSIR-JUNE 2012]

(a) Only a σ –donor
(b) Only π donor
(c) Both a σ -donor and π -donor
(d) A σ -donor and a σ –acceptor
22. The correct d-electron configuration showing spin-orbit coupling is

[CSIR-JUNE 2012]
(a) t42g e2g
(b) t62g e0g
(c) t42g e0g
(d) t32g e2g
23. The nucleophilic attack on olefins under mild conditions:

[CSIR-JUNE 2012]
(a)Is always facile
(b)Is more facile than electrophilic attack on olefins
(c) Is facile for electron-rich olefins
6
(d) Requires activation by coordination to metal.
24. The number of spin-allowed ligand field transitions for octahedral Ni(II) complexes with 3A2g,
ground state is: [CSIR-JUNE 2012]
(a) Two
(b) Three
(c) One
(d) Four
25.The number of microstates for d5 electron configuration is: [CSIR-JUNE 2012]

(a) 21×6³
(b) 14×63
(c) 7×62
(d) 28×63
26. The set of allowed electronic transitions among the following is:
[CSIR-JUNE 2012]
(Α) 4Σ →2Π (B) 3Σ→3Π (C)1Δ→1Δ (D)2Π→ 2Π (E) 3Σ→3Δ
(a) A, B, E
(b) A, C, E
(c) B, C, D
(d) C, D, E
27 In [Mo2(S2)6]-2, cluster the number of bridging 𝐒𝟐$𝟐 and coordination number of Mo

respectively, are [CSIR-DEC 2012]
(a) 2 and 8
(b) 2 and 6
(c) 1 and 8
(d) 1 and 6
28. The light pink color of [Co(H2O)6] +2and the deep blue color of [CoCl4]-2 are due to
[CSIR-DEC 2012]
(a) MLCT transition in the first and d-d transition in the second
(b) LMCT transition in both
(c) d-d transitions in both.
(d) d-d transition in the first and MLCT transition in the second.
29. The number of possible isomers of [Ru(PPh3)2 (acac)2](acac = acetylacetonate) is:

[CSIR-DEC 2012]
(a) 2
(b) 3
(c) 4
(d) 5
7
30. The total number of Cu-O bonds present in the crystalline copper(II) acetate monohydrate is:
[CSIR-DEC 2012]
(a) 10
(b) 6
(c) 8
(d) 4
31. The electric dipole allowed transition in a d² atomic system is

[CSIR-DEC 2012]
(a) 3F→1D
(b) 3F→ 1P
(c) 3F→ 3D
(d) 3F→ 3P
32. Coordination number of "C" in Be2C3 whose structure is correlated with that of CaF2 is:
[CSIR-DEC 2012]
(a) 2
(b) 4
(c) 6
(d) 8
33. In the solid state, the CuCl5 ion has two types of bonds. These are
[CSIR-DEC 2012]
(a) Three long and two short
(b) Two long and three short
(c) One long and four short
(d) Four long and one short
34. The correct spinel structure of Co3O4 is:

[CSIR-DEC 2012]
+2 +3
(a) (Co ) t (2CO ) o O4
(b) (Co+2) t (2Co+3 Co+3) o O4
(c) (Co+2 Co+3) t (Co+3) o O4
(d) (2Co+3) t (Co+2) o O4
35. The platinum complex of NH3 and Cl- ligands is an anti-tumour agent. The correct isomeric
formula of the complex and its precursor are:
[CSIR-DEC 2012]
(a) cis-Pt(NH3) 2Cl2 and PtCl42-
(b) trans-Pt(NH3)2Cl2 and PtCl42-
(c) cis-Pt(NH3) 2Cl2 and Pt(NH3)42-
(d) trans-Pt(NH3) 2Cl2 and Pt(NH3)42-
36. One of the excited states of Ti has the electric configuration [Ar] 4s2 3d1 4p1. The number of
microstates with zero total spin (S) for this configuration is
[CSIR-DEC 2012]
8
(a) 9
(b) 15
(c) 27
(d) 60
37. The rate of exchange of OH2 present in the coordination sphere by 18OH2 of, (i)[Cu(OH2)6]2+
(ii) [Mn(OH2)6]2+ (iii) [Fe(OH2)]62+ (iv) [Ni(OH2)]6 2+ follows an order
[CSIR-DEC 2012]
(a) (i)>(ii)> (iii)> (iv)
(b) (i)>(iv)> (iii) > (ii)
(c) (ii) >(iii) >(iv) > (i)
(d) (iii)> (i)>(iv) >(ii)
38. The reaction of Pt(NH3)42- with two equivalents of NH3 produces

[CSIR-JUNE 2013]
(a) cis-[Pt(NH3) 2Cl2]
(b) trans –[Pt(NH3) 2Cl2]
(c) both cis-[Pt(NH3) 2Cl2] and trans –[Pt(NH3) 2Cl2]
(d) cis –[Pt(NH3) 2Cl4]2-
39.The electronic transition responsible for the colour of the transition metal ions is
[CSIR-JUNE 2013]
(a) dπ →dσ
(b) dπ →dσ*
(c) dπ→ dπ*
(d) dσ → dπ*
40. The Mulliken symbols for the spectroscopic states arising from the free-ion term F are
[CSIR-JUNE 2013]
(a) T2g + Eg
(b) T₁g +T2g + T₁u
(c) T₁g +T2g + A2g
(d) A1g +T2g +T1g
41. Which of the pairs will generally result in tetrahedral coordination complexes, when ligands
are Cl- or OH-.
(A) Be(II), Ba(II)
(B) Ba(II), Co(II)
(C) Co(II), Zn(II)
(D) Be(II), Zn(II)
[CSIR-JUNE 2013]
(a) A and B
(b) B and C
(c) C and D
(d) A and D
9
42. Silica gel contains [Co(Cl4)]2- as an indicator. When activated , silica gel becomes dark blue
while upon absorption of moisture, its colour changes to pale pink This is because,
[CSIR-JUNE 2013]
(a) Co (II) changes its coordination from tetrahedral to octahedral.
(b) Co(II) changes its oxidation state to Co(III)
(c) Tetrahedral crystal field splitting is NOT equal to octahedral crystal field splitting
(d) Co(II) forms kinetically labile while Co(III) forms kinetically inert complexes.
43.Intense band at 15000 cm-1 in the UV-visible spectrum of [Bu4N]2 Re2 Cl8 is due to the
transition
[CSIR-JUNE 2013]
(a) π→π*
(b) δ→ δ*
(c) δ → π*
(d) π→ δ*
Correct answer is (b)
44. Identify the order representing increasing π -acidity of the following ligands C2F4, NEt3, CO
and C2H4
[CSIR-JUNE 2013]
(a) CO < C2F4 < C2H4 < NEt3
(b) C2F4 < C2H4 < NEt3 < CO
(c) C2H4 < NEt3 < CO < C2F4
(d) NEt3 < C2H4 < C2F4 <CO
45. The species with highest magnetic moment (spin only value) is
[CSIR-JUNE 2013]
4-
(a) VCl6
(b) (η5-C5H5)2 Cr
(c) [Co(NO2) 6] 3-
(d) [Ni(EDTA)] 2-
46. Three bands in the electronic spectrum of [Cr(NH 3) 6,] 3+ are due to the following transitions
(A) 4A 2g→ 4T 1g (B) 4A 2g→4T 2g (C) 4A 2g→2E g
Identify the correct statement about them

[CSIR-JUNE 2013]
(a) Intensity of (A) is lowest
(b) Intensity of (C) is lowest
(c) Intensitites of (A), (B) and (C) are similar
(d) Intensities of (B) and (C) are similar
47. The ∆t of the following complexes

(A) [Co(Cl4)]2-
(B) [Co(Br4)]2-
10
(C) [Co(NCS4)]2-
follows the order [CSIR-JUNE 2013]
(a) C>A>B
(b) A> B>C
(c) B>A>C
(d) C> B>A
48. An octahedral metal ion M+2 has magnetic moment of 4.0 B.M. The correct combination of
metal ion and d-electron configuration is given by
[CSIR-DEC 2013]
(a) Co2+, t52g e2g
(b) Cr2+, t42g e2g
(c) Mn2+, t32g e1g
(d) Fe2+, t42g e2g
49. For an electronic configuration of two non-equivalent π electronics [π1, π1] which of the
following terms is not possible?
[CSIR-DEC 2013]
(a) 1Σ
(b) 3Σ
(c) 3Δ
(d) 3𝛟
50. Among the following, the correct combination of complex and its color is
[CSIR-DEC 2013]
Complex Colour
(a) [Co(CN4)]2- Red
(b) [Co(Cl4)]2- Orange
(c) [Co(CNS)4]2- Blue
(d) [Co(F4)]2- Yellow
51. MnCr2O4 is likely to have a normal spinel structure because

[CSIR-DEC 2013]
2+
(a) Mn will have a LFSE in the octahedral site whereas the Cr will not
(b) Mn is +2 oxidation state and both the Cr are in +3 oxidation state.
(c) Mn is +3 oxidation state and I Cr is in +2 and the other is in +3 state.
(d) Cr3+ will have a LFSE in the octahedral site whereas the Mn2+ ion will not.
52. Compounds K2Ba[Cu(NO2) 6] (A) and Cs2Ba[Cu(NO2)6] (B) exhibit tetragonal elongation and
tetragonal compression, respectively. The unpaired electron in A and B are found respectively, in
orbitals
[CSIR-DEC 2013]
2 2
(a) dz² and d x -y ,
11
(b) d x2-y2 and dz²

(c) dz² and dz²
(d) d x2-y2 and d x2-y2
53. The most appropriate structure for the complex [Pt2(NH3)2(NCS)2(PPh3)2] is
(a)
(b)
(c)
(d)
54. In bis(dimethylglyoximato)nickel(II), the number of Ni-N, Ni-O and intramolecular hydrogen

bond(s)respectively are
[CSIR-JUNE 2014]
(a) 4,0 and 2
(b) 2, 2 and 2
(c) 2, 2 and 0
(d) 4, 0 and 1
55. NiBr2 reacts with (Et)(Ph2)P at -78°C in CS2 to give red compound 'A', which upon standing at
room temperature turns green to give compound, 'B' of the same formula. The measured
magnetic moments of 'A' and 'B' are 0.0 and 3.2 BM, respectively. The geometries of 'A' and 'B'
are
[CSIR-JUNE 2014]
(a) square planar and tetrahedral
(b) tetrahedral and square planar
(c) square planar and octahedral
(d) tetrahedral and octahedral
12
56. If L is a neutral mono-dentate ligand, the species, [AgL4]2+ , [AgL6]2+ and [AgL4] 3+
respectively are
[CSIR-JUNE 2014]
(a) Paramagnetic, paramagnetic and diamagnetic
(b) Paramagnetic, diamagnetic and paramagnetic
(c) Diamagnetic, paramagnetic and diamagnetic
(d) Paramagnetic, diamagnetic and diamagnetic
57. [CoL6] 3+ is red in colour whereas [CoL‫׳‬6] 3+ is green. L. and L' respectively corresponds to,
[CSIR-JUNE 2014]
(a) NH3 and H2O
(b) NH3 and 1, 10-phenanthroline
(c) H2O and 1, 10-phenanthroline
(d) H2O and NH3
58. In its electronic spectrum, [V(H₂O) 6] 3+ exihibits two absorption bands, one at 17,800 (v1) and
the second at 25, 700 (v2) cm. The correct assignment of these bands, respectively, is
[CSIR-JUNE 2014]
(a) v1 = ³T₁g (F)→ ³T₂g (F), v₂ = ³T₁g (F) →³T₁g (P)
(b) v1 = ³T₁g (F) →³T₁g (P), v2 = ³T₁g (F) →³T₂g (P)
(c) v1 = ³A2g → ³T₁g (F ), v2= ³A2g → ³T₂g (F)
(d) v1 = ³A2g →³T₂g (F) , v2 = ³A2g →³T₁g ( (F)
59. The term symbol that is NOT allowed for the np2 configuration is
[CSIR-JUNE 2014]
(a) 1D
(b) 3P
(c) 1S
(d) 3D
60. Reaction of [Ru(NH3)5(isonicotinamide)]+3 with [Cr(H2O)6] +3 occurs by inner sphere

mechanism and rate of the reaction is determined by dissociation of the successor complex. It is
due
[CSIR-JUNE 2014]
(a) Inert ruthenium birdged to inert chromium centre
(b) Inert ruthenium bridged to labile chromium centre
(c) Labile ruthenium bridged to inert chromium centre
(d) Labile ruthenium bridged to labile chromium centre
61. Consider the second order rate constants for the following outer-sphere electron transfer
[Fe(H₂O)6] +3 / [Fe(H₂O)6] +2 4.0 M-1 sec-1
13
[Fe(phen) 3] +3 /[Fe(phen) 3] +3 3.0 x107 M-1

(phen= 1, 10-phenanthroline)
The enhanced rate constant for the second reaction is due to the fact that
[CSIR-JUNE 2014]
(a) The 'phen' is a π-acceptor ligand that allows mixing of electron donor and acceptor orbitals
that enhances the rate of electron transfer
(b) The phen' is a π -donor ligand that enhances the rate of electron transfer
(c) The 'phen' forms charge transfer complex with iron and facilitates the eletron transfer
(d) The 'phen' forms kinetically labile complex with iron and facilitates the electron transfer.
62. A 1: 2 mixture of Me₂NCH₂CH₂CH₂PPh₂ and KSCN with K₂[PdCl4] gives a square planar
complex A. Identify the correct pairs of donor atoms trans to each other in complex A from the
following combinations.
[CSIR-JUNE 2014]
(a) P, N
(b) N, S
(c) P, S
(d) N, N
63. Identify the correct statement about [Ni(H₂O) 6]+2 and [Cu(H₂O) 6]+2
[CSIR-JUNE 2014]
(a) All Ni-O and Cu-O bond lengths of individual species are equal
(b) Ni-O(equatorial) and Cu-O(equatorial)
(c) All Ni-O bond lengths are equal whereas Cu-O (equatorial) bonds are shorter than Cu-
O(axial) bonds
(d) All Cu-O bond lengths are equal whereas Ni-O(equatorial) bonds are shorter than Ni-
O(axial)bonds
64. Reaction of nitrosyl tetrafluoroborate to Vaska's complex gives complex A with angle M-N-
O=124°.
The complex A and its N-O stretching frequency are, respectively
[CSIR-JUNE 2014]
-1
(a) [IrCl(CO)(NO)(PPh3)2]BF4, 1620 cm
(b) [IrCl(CO)(NO)2(PPh3)](BF4)2 , 1730 cm-1
(c) [IrCl(CO)(NO)2(PPh3)](BF4)2 1520 cm-1
(d) [IrCl(CO)(NO)(PPh3)2], 1820 cm-1
65. The S and L values for 15N atom respectively, are [CSIR-DEC 2014]
(a) 1/2 and 1
(b)1/2 and 0
(c) 1 and 0
(d) 3/2 and 0
66. In the following reaction [PtCl4]-2 +NO2-, is →A + NH3 →B , compound B is

[CSIR-DEC 2014]
14
-
(a) trans-[PtCl2(NO2)(NH3)]
-
(b) cis-[PtCl(NO2)(NH3)]
(c) trans-[PtCl2(NH3)2]
(d) cis-[PtCl3(NO2)2] -2
67. The number of stereoisomers of trans-[CoCl2(triethylenetetraamine)]Br is

[CSIR-DEC 2014]
(a) One
(b) Two
(c) Three
(d) Four
68. An aqueous solution of [Mn(H2O)6] +2 complex is pale pink in colour. The probable reasons for
it are [CSIR-DEC 2014]
6
(A) Presence of A1g ground state
(B) Disallowed transition by spin selection rule
(C) Presence of 2T2g ground state
(D) Charge transfer transition
The correct answer is

(a) A and B
(b) A and C
(c) B and C
(d) C and D
69.Base hydrolysis of [CoCl(NH3)5] +2 is an overall second order reaction, whereas that of

[Co(CN)] -3 is of first order. The rates depend in both cases solely on the concentrations of the
cobalt complex. This may be due to
(A) Presence of ionizable proton in [CoCl(NH3) 5] +2 but not in [Co(CN) 6]-3,

(B) SN1CB mechanism in the case of [CoCl(NH3) 5] +2 only
(C) SN1CB mechanism in the case of [Co(CN) 6]-3, only
(D) SN1CB mechanism in both the complexes
[CSIR-DEC 2014]
Correct explanation(s) is/are
(a) A and B
(b) A and C
(C) B only
(d) A and D
70. The configuration [Ne] 2p1 3p1 has a 3D term. Its levels are
[CSIR-DEC 2014]
(a) 3D3/2 , 3D1/2
(b) 3D5/2, 3D3/2, 3D1/2
(c) 3D3 , 3D2 , 3D1
(d) 3D3 , 3D2 , 3D1, 3D0
15
71. The spin-only magnetic moment and the spectroscopic ground state term symbol of manganese
center in [MnF6] -3 ion respectively, are
[CSIR-DEC 2014]
(a) 4.9 BM and 5D
(b) 4.9 BM and 4F
(c) 3.9 BM and 3D
(d) 4.9 BM and 3F
72. The three dimensional structure of compound [Co(Co(NH3)4(OH)2)3]Br6 , has

[CSIR-DEC 2014]
(a) Twelve Co-O and twelve Co-N bonds
(b) Ten Co-O and ten Co-N bonds
(c) Fourteen Co-O and ten Co-N bonds
(d) Twelve Co-O and ten Co-N bonds
73. The spin-only and spin plus orbital magnetic moments of [CrCl6]-3 are
[CSIR-DEC 2014]
(a) 3.87 BM and 5.20 BM
(b) 2.84 BM and 5.20 BM
(c) 3.87 BM and 6.34 BM
(d) 2.84 BM and 6.34 BM
74. In transition metal phosphine (M-PR3) complexes, the back-bonding involves donation of
electrons from
[CSIR-JUNE 2015]
(a) M(t2g )→ PR3(σ*)
(b) M(t2g ) →PR3 (π*)
(c) M(eg )→ P(d)
(d) PR3 ( π ) →M(t2g )
75. The electric-dipole allowed transition among the following is

[CSIR-JUNE 2015]
(a) 3S → 3D
(b) 3S →3P
(c) 3S →1D
(d) 3S →1F
76. The lowest energy-state of an atom with electronic configuration ns1np1 has the term symbol
[CSIR-JUNE 2015]
(a) ³P1
(b) 1P1
(c) 3P2
(d) 3P0
16
77. Match the complexes given in column I with the electronic transitions (mainly responsible for
their colours) listed in column II
Column-I Column-II
(I) Fe(II)-protoporphyrin IX (A) π →π*
(II) [Mn(H₂O)6]Cl2 (B) spin allowed d-d
(III) [Co(H₂O)6]Cl2 (C) spin forbidden d→d
(D) M→ L charge transfer
The correct answer is:
[CSIR-JUNE 2015]
(a) I-A, II-C and III-B
(b) I-D, II-B and III-C
(c) 1-A, II-C and III-D
(d) I-A, II-B and III-C
78. Among the complexes, (A) K 4[Cr(CN) 6] , K 4[Fe(CN) 6] , (C) K 3[Co(CN) 6] , (D)K 4
[Mn(CN)6],and Jahn-Teller distortion is expected in
[CSIR-JUNE 2015]
(a) A, B and C
(b) B, C and D
(c) A and D
(d) B and C
79. The complex [Fe (phen) 2(NCS) 2] (phen 1,10-phenanthroline) shows spin cross-over behaviour
CFSE and at µeff 250 and 150K, respectively are
[CSIR-JUNE 2015]
(a) 0.4Δ0 , 4.90 BM and 2.4Δ,, 0.00 BM
(b) 2.4Δ0 , 2.90 BM and 0.4Δ, 1.77 BM
(c) 2.4Δ0 , 0.00 BM and 0.4Δ, 4.90 BM
(d) 1.2Δ0, 4.90 BM and 2.4Δ. 0.00 BM
80. The term symbol for the first excited state of Be with the electronic configuration 1s2 2s1 3s1 is.
[CSIR-DEC 2015]
(a) 3S1
(b) 3S0
(c) 1S0
(d) 2S1/2
81. The oxidizing power of [CrO4]2- , [MnO4]2- and [FeO4]2- follows the order
[CSIR-DEC 2015]
(a) [CrO4]2-< [MnO4]2- < [FeO4]2-
(b) [FeO4]2- < [MnO4]2- <[CrO4]2-
(c) [MnO4]2- < [FeO4]2- < [CrO4]2-
(d) [CrO4]2- < [FeO4]2- < [MnO4]2-
82. Using crystal field theory, identify from the following complex ions that shows same µeff (spin
only) values
17
(A) [CoF6] 3-
(B) [IrCl6] 3-
(C) [Fe(H2O) 6] 2+
[CSIR-DEC 2015]
(a) A and B
(b) B and C
(c) A and C
(d) A, B and C
83. The correct statement for Mn-O bond lengths in [Mn(H2O)6 ] 2+ , is

[CSIR-DEC 2015]
(a) all bonds are equal
(b) four bonds are longer than two others
(c) two bonds are longer than four others
(d) they are shorter than the Mn-O bond in [MnO4]-
84. Identify the complex ions in sequential order when ferroin is used as an indicator in the
titration of iron(II) with potassium dichromate, (phen = 1, 10-phenathroline)
[CSIR-DEC 2015]
2+ 3+
(a) [Fe(phen) 3] and [Fe(phen) 3]
(b) [Fe (phen) 3] 3+ and [Fe(phen) 3 ] 2+
(c) [Fe(CN) 6] 4- and [Fe(CN) 6] 3-
(d) [Fe(CN)6] 3- and [Fe(CN) 6] 4-
85. The formation constant for the complexation of M+ (M= Li, Na, K and Cs) with cryptand,
C222 follows the order
[CSIR-DEC 2015]
(a) Li+ <Cs+ < Na+ < K+
(b) Li+< Na+ <K+ <Cs+
(c) K+ <Cs+ <Li+ < Na+
(d) Cs+ <K+ <Li+ < Na+
86. [MnO4] - is deep purple in colour whereas [ReO4] - is colourless. This is due to
greater energy required for
[CSIR-DEC 2015]
(a) d-d transitions in the Re compound compared to the Mn compound
(b) d-d transitions in the Mn compound compared to the Re compound
(c) charge transfer from O to Re compared to O to Mn
(d) charge transfer from O to Mn compared to O to Re
87. The correct statement about the substitution reaction of [Co(CN) 5Cl] 3- with OH- to give
[Co(CN)5(OH)] 3- is,
[CSIR-DEC 2015]
(a) it obeys first order kinetics
(b) its rate is proportional to the concentration of both the reactants
(c) it follows the SN1CB mechanism
18
(d) its rate is dependent only on the concentration of [OH] -
88. Aqueous Cr+2 effects one electron reduction of [Co(NH3)5Cl] +2 giving compound Y. Compound
Y undergoes rapid hydrolysis. Y is,
[CSIR-DEC 2015]
(a) [Co(NH3)5]+2
(b) [Co(NH3)5(OH) ]+
(c) [Co(NH3)4(OH)2]
(d) [Cr(H2O)5Cl]+2
89. Choose the correct statements about Tanabe-Sugano diagrams

(A) E/B is plotted against Δ0/B.
(B) The zero energy is taken as that of the lowest term
(C) Terms of the same symmetry cross each other
(D) Two terms of the same symmetry upon increases of ligand field strength bend apart from each
other.
[CSIR-DEC 2015]
Correct answer is
(a) A and B
(b) A and C
(c) A, B and D
(d) A, B, C and D
90. Three electronic transitions at 14900, 22700 and 34400 cm-1 are observed in the absorption
spectrum of [CrF6] -3 , The Δ0 value (in cm-1) and the corresponding transition are
[CSIR-DEC 2015]
4 4
(a) 7800 and A2g → T₂g
(b) 14900 and 4A2g →4T₂g
(c) 14900 and 4T₁g →4T₁g (F)
(d) 7800 and 4T2g →³T1g (F)
91. Possible term symbol(s) of the excited states of Na atom with the electronic configuration [1s2
2s2 2p6 3p1] is/are
[CSIR-DEC 2015]
(a) 2S1/2
(b) 2P3/2 and 2P1/2
(c) 1S0 and 1P1
(d) 3P0 and 3P1
92. The symmetry-allowed atomic transition among the following is

[CSIR-DEC 2015]
(a) 3F→ 1D
(b) 3F→ ³D
(c) 3F→ 1P
(d) ³F→ ³P
19
93. [NiIIL6] n+ or n- shows absorption bands at 8500, 15400, and 26000 cm-1 whereas
[NiII Lʹ6] n+ or n- at 10750, 17500 and 28200 cm-1 . L and L' are respectively
[CSIR-JUNE 2016]
-1 $𝟏
(a) OH and 𝐍𝟑
(b) Cl-1 and I-1
(c) NCS-1 and RC𝐎$𝟏 𝟐
(d) H2O and NH3
94. The number of microstates present in 3F-term is [CSIR-JUNE 2016]

(a) 3
(b) 21
(c) 9
(d) 28
95. Chelate effect is [CSIR-JUNE 2016]

(a) predominantly due to enthalpy change
(b) predominantly due to entropy change
(c) independent of ring size
(d) due to equal contribution of entropy and enthalpy change
96. The lowest energy term for the d6 configuration is [CSIR-JUNE 2016]
(a) 2D
(b) 5D
(c) 1P
(d) 1D
97. The first excited state of hydrogen molecule is [CSIR-JUNE 2016]

(a) 1∑.
𝒈
(b) 1∑.
𝒖
(c) 3∑$
𝒈
(d) 3∑.
𝒖
98. Complex [Cr(bipyridyl)3]+3 , shows red phosphorescence due to transition

[CSIR-JUNE 2016]
(a) 4T2g ← 4A2g
(b) 4T1g ← 4A2g
(c) 4A2g ← 2Eg
(d) 2Eg ← 4A2g
99. The complex that shows orbital contribution to the magnetic moment, is
[CSIR-JUNE 2016]
+2
(A) [Cu(H2O)6]
(B) [Ni(H2O)6]+2
20
(C) [Co(H2O)6] +2
(D) [Cr(H2O)6]+2
100. Paramagnetic susceptibility of the order of 10-6 cm3 mol-1 observed for KMnO4 is due to-
[CSIR-JUNE 2016]
(a) random spin alignment
(c) paramagnetic impurity
(b) antiferromagnetic exchange interaction
(d) temperature independent paramagnetism
101. The room temperature magnetic moment ( in BM) for a monomeric Cu(II) complex is greater
than 1.73. This may be explained using the expression: [CSIR-JUNE 2016]
𝝀𝜶
(A) µeff = µs 𝟏 −
𝚫
(B) µeff = 𝒏 𝒏 + 𝟐
(c) µeff = 𝟒𝒔 𝒔 + 𝟏 + 𝑳(𝑳 + 𝟏)
(d) µeff = g 𝑱 𝑱 + 𝟏
102. The HOMO (highest occupied molecular orbital) to LUMO (lowest unoccupied molecular
orbital) electronic transition responsible for the observed colours of halogen molecules (gas) is
[CSIR-DEC 2016]
(a) π*→ σ*
(b) π* → π*
(c) σ → σ*
(d) π→ σ*
103. In the hydrolysis of trans-[Co(en)2Cl(A)]+ if the leaving group is chloride, the formation of cis
product is the least, when A is [CSIR-DEC 2016]
-
(a) NO2
(b) NCS-
(c) Cl-
(d) OH-
104. The nephelauxetic parameter β is highest for [CSIR-DEC 2016]

(a) Br-
(b) Cl-
(c) CN-
(d) F-
105. The 2Eg ←4A2g transition in the electronic spectrum of [Cr(NH3)6]+3 occurs nearly at
[CSIR-DEC 2016]
(a) 650 nm
21
(b) 450 nm
(c) 350 nm
(d) 200 nm
106. For [Ce(NO3)4(OPPh3)2] from the following

A. Its aqueous solution yellow-orange in
B. Coordination number of Ce is ten
C. It shows metal to ligand charge transfer
D. It is diamagnetic in nature
The correct answer is [CSIR-DEC 2016]
(a) A and B
(b) A and C
(c) A, B and D
(d) B, C and D
107. Consider the following statements for [FeO4]-4

A. It is paramagnetic
B. It has Td symmetry
C. Adopts distorted square planar geometry
D. Shows approximately D2d symmetry
The correct answer is [CSIR-DEC 2016]
(a) A, B and C
(b) A, C and D
(c) A and D
(d) A and B
108. The spectroscopic ground state term symbols for the octahedral aqua complexes of Mn(II),
Cr(III) and Cu(II), respectively, are [CSIR-DEC 2016]
2 4 2
(a) H , F and D
(b) 6S, 4F and 2D
(c) 2H , 2H and 2D
(d) 6S, 4F and 2P
109. For OH- catalysed SN 1 conjugate base mechanism of [Co(NH3)5Cl]+2, the species obtained in
the first step of the reaction is/are [CSIR-DEC 2016]
(a) [Co(NH3)5(OH)]+2 +Cl-
(b) [Co(NH3)4(NH2)Cl]+ +H2O
(c) [Co(NH3)4(NH2)]+2 +CI
(d) [Co(NH3)5Cl(OH)]+only
110. In the following redox reaction with an equilibrium constant K = 2.0 x 108
[Ru(NH3)6]+2 +[Fe(H2O6)]+3 →[Ru(NH3)6]+3 +[Fe (H2O)6]+2
the self exchange rates for oxidant and reductant are 5.0 M-1s-1 and 4.0x103 M-1s-1 respectively.
The approximate rate constant (M-1s-1) for the reaction is
[CSIR-DEC 2016]
(a) 3.16x106
22
(b) 2.0x106
(c) 6.32x106
(d) 3.16x106
111. The correct statement for a Fischer carbene complex is [CSIR-DEC 2016]
(a) the carbene carbon is electrophilic in nature
(b) metal exists in high oxidation state
(c) metal fragment and carbene are in the triplet states
(d) CO ligands destabilize the complex
112. The highest molecular orbitals for an excited electronic configuration of the oxygen molecule
are [ 1πg ]1 [3ϭu]1. A possible molecular term symbol for oxygen with this electronic configuration
is
[CSIR-DEC 2016]
(a) 1π
(b) 3∑
(c) 1∆
(d) 1∑
113. CdS , HgS and BiI3 are coloured due to [CSIR-JUNE 2017]
(a) L→M charge transfer transitions
(b) d→ d electronic transitions
(c) M→L charge transfer transitions
(d) combination of L →M charge transfer and d→d electronic transitions
114. The relative rates of water exchange for the hydrated complexes of
(1) Ni+2 (2) V+2 and (3) Cr³+ ions follows the trend: [CSIR-JUNE 2017]
(a) (1) > (2) > (3)
(b) (1) < (2) < (3)
(c) (1) > (2) < (3)
(d) (1) < (2) > (3)
115. Consider the following sulfur donor atom bearing bidentate ligand where X and name of
ligands are given in following columns
X Ligand name
A. NR2 I. Dithiocarbonate
B. OR II. Dithiocarbamate
C. O- III. Xanthate
D. SR IV. Thioxanthate
23
Correct match of entries given in two columns is [CSIR-JUNE 2017]

(a) A-II, B-III, C-I, D-IV
(c) A-I, B-II, C-III, D-IV
(b) A-III, B-II, C-IV, D-I
(d) A-IV, B-I, C-II, D-III
116. A copper (II) complex having distorted octahedral geometry shows an absorption band at 625
nm. Given spin-orbit coupling of the complex as 625 cm-1, the µeff (in B.M.) is
[CSIR-JUNE 2017]
(a) 1.73
(b) 1.81
(c) 1.63
(d) 1.93
117. Consider the following statements for octahedral complexes. (a) [CrF6]-3 (b) [Cr(ox)3]-3 and
(c)[Cr(en)3]+3
A. their d→d transitions are at 14900, 17500, and 21800 cm-1, respectively
B. their spin-only magnetic moments are same
C. two of them have optical isomers
D. all of them show Jahn-Teller distortion
The correct statements are [CSIR-JUNE 2017]
(a) A, B, and C
(b) A, C, and D
(c) B, C, and D
(d) B and D
118. Match the items in the three columns.
The correct answer is [CSIR-JUNE 2017]

(a) A-II-X; B-I-Z; C-III-Y
(c) A-III-Y: B-1-Z; C-II-X
(b) A-I-X; B-Il-Y; C-III-Z
(d) A-I-X; B-II-Z; C-III-Y
119. For the following complexes, the increasing order of magnetic moment (spin only value) is
A. [TiF6]-3
B. [CrF6]-3
C. [MnF6]-3
24
D. [CoF6]-3 [CSIR-DEC 2017]

(a) D<A<B<C
(b) C<A<D<B
(c) B≈ A<D<C
(d) A<B<C≈ D
120. The geometry around Cu and its spin state for K3CuF6 and KCuL2 , [H2L= H2
NCONHCONH2], respectively are: [CSIR-DEC 2017]
(a) (octahedral, high-spin) and (square planar, low-spin)
(b) (octahedral, low-spin) and (square planar, low-spin)
(c) (trigonal prismatic, high-spin) and (tetrahedral, high-spin)
(d) (trigonal prismatic, low-spin) and (tetrahedral, high-spin)
121. Consider the following statements with respect to the base hydrolysis of [CoCl(NH3)5] to
[Co(NH3)5(OH)]+2
A. One of the ammonia ligands acts as a Bronsted acid.
B. The entering group is water.
C. A heptacoordinated Co+3 species is an intermediate.
The correct statement(s) is/are [CSIR-DEC 2017]
(a) A and B
(b) A and C
(c) B and C
(d) C only
122. Considering the ambidentate behaviour of thiocyanante ion, the most stable structure among
the following is [CSIR-DEC 2017]
(a)
(b)
25
(c)
(d)
123. For high spin and low spin d6 octahedral complexes (ML6), the generally observed spin
allowed transitions respectively, are [CSIR-DEC 2017]
(a) two and one
(b) one and two
(c) zero and one
(d) two and two
124. Br2 with propanone forms a charge transfer complex and I2 forms triiodide anion with I- .
This implies that [CSIR-DEC 2017]
(a) both Br2 and I2 act as bases
(b) both Br2 and I2 act as acids
(c) Br2 acts as an acid and I2 acts as a base
(d) Br2 acts as a base and I2 acts an an acid
125. Mismatch among the following is [CSIR-DEC 2017]

(a) Sharp transition and fluorescence in lanthanides
(b) Broad bands and d-d transitions
(c) Very high spin-orbit coupling and transition elements
(d) Charge transfer and molar absorptivity of the order of 10¹ L mol-1cm-1
126. The total degeneracy of the ground term of Co11 (high spin) in octahedral geometry is
[CSIR-JUNE 2018]
1. 18
2. 12
3. 28
4.9
26
127. High spin complex of a 3d metal ion M has a magnetic moment of 2.9 B.M. in octahedral
coordination environment and 4.1 B.M. in tetrahedral environment. The M ion is
[CSIR-JUNE 2018]
+2
1. Co
2. Ni+2
3. Cu+2
4. Co+2
128. For electronic spectra of K2CrO4 (A) and K2MoO4 (B) the correct combination is
[CSIR-JUNE 2018]
1. Transition is d-d and λmax has for A <B
2. Transition is LMCT and λmax for A <B
3. Transition is LMCT and λmax for A > B
4. Transition is MLCT and λmax for A > B
129. The lowest energy state of a 1s1 2s1 electronic configuration, according to hund's rule, is
[CSIR-JUNE 2018]
3
1. S0
2. 1S0
3. 3S1
4. 1S1
130. Consider the following statements:

(A) Cr+2 is easier to oxidize than V+2 in the gas phase
(B) Cr+2 (aq) is a more powerful reducing agent than V+2 (aq).
(C) The rate of water exchange for Cr+2 (aq) is much faster than for V+2(aq)
1. A and B
2. A and C
3. B and C
4. A, B and C
131. Consider the statements A - D regarding equation I-III:

(1) [Fe(CN)6]-3 + [Co(CN)5]-3 → [Fe(CN)6]-4 + [Co(CN)5]-2
(II) [Co(bipy)3]+2 + [Co* (bipy)3]+3 → [Co(bipy)3]-3 +[Co*(bipy)3]+2
(III) [Co(NH3)F]+2 + [CrH2O)6]+2 → [Co(NH3)5(H2O)]+2 + [Cr(H2O)5F]+2
(A) Marcus equation is applicable to I and II.
(B) Marcus equation is applicable to II only.
(C) Equation I and II involve inner sphere electron transfer.
(D) Equation I and III involve inner sphere electron transfer.
The correct statements are: [CSIR-JUNE 2018]
1. A and B
2. B and C
27
3. B and D
4. C and D
132. The allowed electronic transition in fluorine molecule is [CSIR-JUNE 2018]

Ι. ∑.
𝒈 → ∑𝒈
.
2. ∑.
𝒈 → ∑𝒈
.
3. ∑.
𝒈 → πu
4. ∑.
𝒈 →∆u
133. Consider the species NO , I2 , I2- , Cu+2 and VO+2 . The number of paramagnetic species
among them and the EPR inactive species, respectively, are [CSIR-DEC 2018]
(a) 4 and I2-
(b) 4 and I2
(c) 3 and VO+2 , Cu+2
(d) 3 and NO, Cu+2
134. The intermediate [Fe(SCN)(H2O)5]+2 is detected in the reaction of [Co(NCS)(NH3)5]+2 with

[Fe(H2O)6]+2 in aqueous medium to produce [Co(H2O)6]+2 and [Fe(H2O)6]+3
The mechanism of the reaction is [CSIR-DEC 2018]
(a)Interchange dissociative
(b) Interchange associative
(c) Inner sphere electron transfer
(d) Outer sphere electron transfer
135. For magnesium complex of EDTA2- , the number of N-donor and O-donor centers, are
respectively. [CSIR-DEC 2018]
(a) two and four
(b) two and two
(c) two and six
(d) two and eight
136. The correct set of electronic configurations for metal ions in octahedral coordination
geometry for strong Jahn-Teller distortion is [CSIR-DEC 2018]
6 1 3 1 6 3
(a) t 2g e g , t 2g e g , t 2g e g
(b) t12g , t32g e2g , t62g e1g
(c) t32g , t32g e1g , t32g e2g
(d) t32g e2g , t62g e2g , t62g e3g
137. The correct order of intensity of the d-d transitions in the complexes of a 3d-transition metal
ion [CSIR-DEC 2018]
(a) cis-[M(H2O)4Cl2] > trans-[M(H₂O)4Cl2] > [M(H₂O)6]+2
(b) [M(H₂O)6]+2 > cis-[M(H₂O)4 Cl2] > trans-[M(H₂O)4Cl₂]
(c) trans-[M(H₂O)4Cl₂] > cis-[M(H₂O)4Cl₂] > [M(H₂O)6]+2
(d) [M(H₂O)6]+2 > cis-[M(H₂O)4Cl2 ] > trans-[M(H₂O)4Cl₂]
28
138. The isomers A and B undergo base hydrolysis by forming a trigonal bipyramidal
intermediate.
The correct statement is
[CSIR-DEC 2018]
(a) A reacts faster than B and both results in a mixture of products
(b) B reacts faster than A and both results in a mixture of products
(c) A reacts fastser than B and B results ini a mixture of products
(d) B reacts faster than A and A results in a mixture of products.
139. Consider the two sets of molecules.

Set A: [AlF6]-3 , [PF6]- , [SF6] and [SiF6]-2
Set B: [ Ba(H2O)6]+2 , [Ca(H2O)6]+2 , [Mg(H2O)6 ]+2, [Sr(H2O)6]+2
The slowest ligand exchange rate in Set A and Set B are, respectively [CSIR-DEC 2018]
(a) [AlF6]-3 and [Sr(H2O)6]+2
(c) [SiF6]-2 and [Ca(H2O)6]+2
(b) [SF6] and [Mg(H2O)6]+2
(d) [PF6]- and [Ca(H2O)6]+2
140. Self-exchange electron transfer is fastest in [CSIR-JUNE 2019]

(a) [Ru(NH3)6 ]+2/+3
(b) [Co(NH3)6] +2/+3
(c) [Cr(OH)6] +2/+3
(d) [Fe(OH2)6] +2/+3
141. Consider the following reaction:

Hg+2 (aq) + X- (aq) = [HgX]+ (aq)
The stability constants for [HgX]+ (aq) for X = F, Cl and Br follow the order
[CSIR-JUNE 2019]
(a) F<Cl< Br
(b) Br<Cl< F
(c) Cl< Br< F
(d) Br< F<Cl
142. The correct set of information is [CSIR-JUNE 2019]

(a) [Mn(H2O)6]+2: µobserved = µspin ;[Co(H2O)6]+3 : Paramagnetic
(b) [Mn(H2O)6]+2: µobserved > µspin ;[Co(H2O)6]+3 : Diamagnetic
29
(c) [Mn(H2O)6]+2: µobserved = µspin ;[Co(H2O)6]+3 : Diamagnetic

(d) [Mn(H2O)6]+2: µobserved > µspin ;[Co(H2O)6]+3 : Paramagnetic
143. Consider the following statements regarding electronic spectra of high spin complexes
(A) Ti+3 complexes exhibit one sharp band.
(B) Co+2 and Cr+3 complexes exhibit two broad bands.
(C) Mn+2 complexes exhibit a series of very weak and sharp bands.
(D) Ni+2 complexes exhibit three broad bands .
(a) A and C
(b) A, C and D
(c) C and D
(d) B, C and D
144. Hydrolysis of trans-[CoLCl(en)2]+ (L= NO2-, NCS-, OH- ,Cl- ) results in a product (A). The
tendency to form cis-isomer of the product (A) follows the order
[CSIR-JUNE 2019]
- - - -
(a) L= NO2 < NCS < OH < Cl
(b) L= NO2- < Cl- < NCS- < OH-
(d) L= OH- < NCS- <Cl- < NO2-
(c) L= OH- <Cl- < NO2- < NCS-
145. Donor mode of NO ligand depends on the metal. Now, consider the following complexes (in
gaseous state).
(A) [IrCl(CO)(PPh3)2(NO)]+
(B) [RuCl(PPh3)2(NO)2]+
(C) [Co(NCS)(diars)2(NO)]+ , where diars →o-(Me2As)2C6H4.
(D) [Cr(CN)5(NO)]3-
The complex (es) that do NOT exhibit bent NO coordination mode is/are
[CSIR-JUNE 2019]
(a) A and B
(b) C and D
(c) D only
(d) B only
146. An aqueous solution of metal ion (A) gives a blood-red colored product (B) upon reaction
with KSCN. Upon dropwise addition of NaF, the complex turns to a colorless compound (C).
Identify A,B and C [CSIR-JUNE 2019]
(a) aq. Fe(II), [Fe(SCN)(H2O)5]+ and [Fe(H2O)6]+2
(b) aq. Fe(III), [Fe(SCN)(H2O)5]+2 and [FeF6 ]+3
(c) aq. Fe(II), [Fe(SCN)(H2O)5]+ and FeF3
(d) aq. Fe(III), [Fe(SCN)3(H2O)3]+ and FeF3
147. Correct order of molar extinction coefficient values of the visible absorption bands for the
following species is
[CSIR-DEC 2019]
30
(1)[Cr(H2O)6]+2 > [Mn(H2O)6]+2 >Chlorophyll >[NiCl4]-2

(2)Chlorophyll > [NiCl4]-2 > [Cr(H2O)6]+2 > [Mn(H2O)6]+2
(3)[NiCl4]-2 > Chlorophyll > [Cr(H2O)6 ]+2 > [Mn(H2O)6]+2
(4)Chlorophyll > [Cr(H2O)6]+2> [NiCl]-2 >[Mn(H2O)6]+2
148. The correct statement about base hydrolysis of [Co(py)4Cl2]+ (py-pyridine) is

[CSIR-DEC 2019]
(1) rate expression is, Rate-k[Co(py)4Cl2]+ [OH-]
(2) reaction does not depend on hydroxide ion concentration
(3)reaction proceeds through SN1CB mechanism
(4)intermediate involved in this reaction is [Co(py)4Cl2(OH)]
149. FeCr2O4 and NiGa2O4 have normal and inverse spinel structures, respectively. The correct
statement is
[CSIR-DEC 2019]
(1) Fe(II) and Ni(II) occupy octahedral sites
(2) Fe (II) and Ni(II) occupy tetrahedral and octahedral sites, respectively
(3) Cr(III) and Ga(III) occupy only octahedral sites
(4) Cr(III) and Ga(III) occupy tetrahedral and octahedral sites, respectively
150. The correct match of spin-only magnetic moment for the complexes cis-[Fe(phen)2 (NCS-N)2]
(A) and [Fe(phen)3]Cl2 (B) at 300 K is (phen=1,10-phenantholine)
[CSIR-DEC 2019]
(1)4.89 BM for both A and B
(2)0 BM for both A and B
(3) 4.89 BM for A and 0 BM for B
(4) 0 BM for A and 4:59 BM for B
151.In the electronic spectrum of [IrBr6]2- , the number of charge transfer band(s) and their origin
are respectively
[CSIR-DEC 2019]
(1)Two ligand→ metal (ϭ → t2g and ϭ →a1g*)
(2)One ligand →metal (ϭ →eg)
(3)Two ligand→ metal (ϭ →t2g and ϭ →eg )
(4)One ligand→ metal (ϭ →t2g)
152. For the given reaction

[*Co(L)n]+2 + [Co(L)n]+3 → [*Co(L)n]+3 + [Co(L)n]+2
the correct statement with respect to the rate of electron transfer process is
o-phen = o-phenanthroline ; *Co is labeled atom [CSIR-2020]
(a) fast electron transfer; L= NH3; n = 6
(b) slow electron transfer ; L = o-phen; n = 3
(c) very slow electron transfer ; L = NH3 ; n = 3
(d) very slow electron transfer: L = o-phen; n = 3
31
153. The number of geometrical isomers of the complex [RhH (C≡CR)2(PMe3)3] is

[CSIR-2020]
(a) 2
(b) 3
(c) 4
(d) 1
154. I2 is violet in the solid as well as in gas phase. However in acetone or ethanol, it turns brown.
Choose the correct statement(s) for this colour change:
(a) Dissociation of I2 in atomic state
(b)Interaction of low-lying ϭ*-orbital of iodine with lone pair of O (solvent)
(c)Formation of a charge-transfer complex [CSIR-2020]
1. (a) only
2. (b) only
3. (a) and (b) only
4. (b) and (c) only
155. The pair of compounds in which both members show LMCT band in their electronic spectra
is [CSIR-2020]
-2 +2
(a) [FeCl4] and [Fe(bpy)3]
(b) [FeBr4]-2 and [TcO4]-
(c) [ReO4]- and [Ru(bpy)]+2
(d) [Fe(phen)3]+2 and [FeCl4]-2
156. For the d3 electron configuration, the ground state term symbol is [CSIR-2020]
(a) 4F1/2
(b) 4F3/2
(c) 4F7/2
(d) 4F9/2
157. The products A and B for the given reaction

[Co(NH3)5Cl]+2 + [Cr(OH2)6]+2 + 5H3O+ → A+B
are respectively, [CSIR-2020]
(a) [Co(OH2)5Cl]+ , [Cr(OH2)6]+3
(b) [Co(NH3)5(OH2)]+2, [Cr(OH2)5Cl]+2
(c) [Co(OH2)6]+2, [Cr(OH2)5Cl]+2
(d) [Co(NH3)5Cl]+ , [Cr(OH2)6]+3
158. The number of expected electronic transitions in [Cr(en)3]+3 and trans-[Cr(en)2F]+ at 4 K is,
respectively (en = ethylenediamine) [CSIR-2020]
a. 3 and 3
b. 3 and 4
c. 3 and 5
d. 3 and 6
159. The value of magnetic moment will be independent of temperature for

32
(acac = acetylacetonato; OAc = acetate; o-phen = o-phenathroline;

Pz = pyrazolyl) [CSIR-2020]
(a) [Fe(acac)3]
(b) [Cu(OAc)4(H2O)2]
(c) [Fe(o-phen)2(NCS)2]
(d) [Fe{(HC(3,5-Me2Pz)3}2]+2
160. In the following sequence of reactions the correct P, Q and R are respectively
[CSIR-2020]
+
(a) KNO2 , CO2 , [Fe(H2O)5S] , HgS
(b) KNO2 , N2, [Fe(H2O)5(SCN)]2+, [Hg(SCN)4]2-
(c)KNO3 , N2, [Fe(H2O)5(CN)]+2 , [Hg(OCN)4]2-
(d) NaN3, N2 , [Fe(H2O)5(N3)]+2 , [Hg(N3)4]2-
161. The term symbol for the ground state of dinitrogen cation radical [CSIR-2020]
(N2)+ is
(a) 2πu
(b) 2∑$𝒖
(c) 2πg
(d) 2∑.𝒈
162.The calculated heat of formation (∆Hf) for NaCl2 and CaF is [CSIR-2020]
(a) negative for both NaCl2 and CaF
(b) negative for NaCl2 but positive for CaF
(c) positive for NaCl2 but negative for CaF
(d) positive for both NaCl2 and CaF
163. Which of the following statements regarding dissociative substitution in an octahedral

transition metal complex,
(1) High steric hindrance between ligands in the metal complex favours fast dissociation of ligand.
(2) Increased charge on the metal atom/ion of the complex favours the acceptance of electron pair
of the entering ligands.
(3) A penta-coordinated intermediate is observed.
(4) Nature of the entering ligand significantly influences the reaction.
Which are correct? [CSIR JUNE 2021]
(a) 1 and 4
(b) 1 and 3
(c) 1, 3 and 4
33
(d) 1, 2, 3 and 4
164. Consider an octahedral complex Ma2b2cd, where 𝒂, 𝒃, 𝒄, and d are monodentate ligands. The
number of enantiomeric pairs for the complex is [CSIR JUNE 2021]
(a) one
(b) two
(c) three
(d) four
165. For the ligand-to-metal charge-transfer (LMCT) transitions in the oxo-anions given below,
the wavelength of the transitions are in the order [CSIR JUNE 2021]
𝟑$ 𝟐$ $ 𝟐$ 𝟐$ 𝟐$
(a) 𝑽𝑶𝟒 < 𝑪𝒓𝑶𝟒 < 𝑴𝒏𝑶𝟒 𝒂𝒏𝒅 𝑾𝑶𝟒 < 𝑴𝒐𝑶𝟒 < 𝑪𝒓𝑶𝟒
(b) 𝑽𝑶𝟑$
𝟒 < 𝑪𝒓𝑶 𝟐$
𝟒 < 𝑴𝒏𝑶 $
𝟒 𝒂𝒏𝒅 𝑾𝑶𝟐$ 𝟐$
𝟒 > 𝑴𝒐𝑶𝟒 > 𝑪𝒓𝑶𝟒
𝟐$
(c) 𝑽𝑶𝟑$ 𝟐$ $ 𝟐$
𝟒 > 𝑪𝒓𝑶𝟒 > 𝑴𝒏𝑶𝟒 𝒂𝒏𝒅 𝑾𝑶𝟒 < 𝑴𝒐𝑶𝟒 < 𝑪𝒓𝑶𝟒
𝟐$ 𝟐$
(d) 𝑽𝑶𝟑$ 𝟐$ $ 𝟐$
𝟒 > 𝑪𝒓𝑶𝟒 > 𝑴𝒏𝑶𝟒 𝒂𝒏𝒅 𝑾𝑶𝟒 > 𝑴𝒐𝑶𝟒 > 𝑪𝒓𝑶𝟒
𝟐$ 𝟐$
166. Consider the following statements for the self-exchange electron transfer reaction in
[Cr(H2O)6]2+/3+ [CSIR JUNE 2021]
A. σ* orbitals are only involved in electron transfer
B. It involves large inner-sphere reorganization energy
C. It involves no change in M–L bond lengths
D. Rate of self-exchange electron transfer is fast
The correct statements are
(a) A, B and D
(b) A and B
(c) A and C
(d) B and D
167. The number of CO bands for isomers from sets (i) and (ii) in their IR spectra
Set (i): Trigonal bipyramidal isomers, axial-𝑭𝒆(𝑪𝑶)𝟒𝑳 (A) and equatorial-𝑭e(𝑪𝑶)𝟒𝑳
(B)
Set (ii): Octahedral isomers, 𝒇𝒂𝒄-𝑴𝒐(𝑪𝑶)𝟑𝑳𝟑 (C) and 𝒎𝒆𝒓-𝑴𝒐(𝑪𝑶)𝟑𝑳𝟑 (D) are
(a) A, 4 and B, 3; C, 3 and D, 2 [CSIR JUNE 2021]
(b) A, 4 and B, 3; C, 2 and D, 3
(c) A, 3 and B, 4; C, 3 and D, 2
(d) A, 3 and B, 4; C, 2 and D, 3
168. The absorption spectrum of [𝑪𝒓(𝑵𝑯𝟑)6]3+ in water shows two bands around 475 and 365 nm.
The ground term and the spin-allowed transitions, respectively, are [CSIR JUNE 2021]
(a) 𝑭; 𝑻𝟏𝒈(𝑭) → 𝑻𝟐𝒈𝒂𝒏𝒅 𝑻𝟏𝒈→ 𝑨𝟐𝒈
𝟒 𝟒 𝟒 𝟒 𝟒
(b) 𝟒𝑭; 𝟒𝑨𝟐𝒈→ 𝟒𝑻𝟐𝒈 𝒂𝒏𝒅 𝟒𝑨𝟐𝒈→ 𝟒𝑻𝟏𝒈(𝑭)

(c) 𝟐𝑮; 𝟐𝑬𝒈→𝟐𝑻𝟏𝒈 𝒂𝒏𝒅 𝟐𝑬𝒈→ 𝟐𝑻𝟏𝒈
(d) 𝟐𝑭; 𝟐𝑨𝟐𝒈 → 𝟐𝑻𝟐𝒈𝒂𝒏𝒅 𝟐𝑨𝟐𝒈→ 𝟐𝑻1𝒈(𝑭)
34
169. For trigonal bipyramidal coordination complex (ML5) the correct point group symmetry and
the relative order of the energies of the 3d orbitals in that crystal field, respectively are
(a) 𝑫𝟑𝒉 ; 𝒅𝒙𝟐−𝒚𝟐 > 𝒅𝒛𝟐, 𝒅𝒙𝒚 > 𝒅𝒙𝒛 , 𝒅𝒚𝒛 [CSIR JUNE 2021]
(b) 𝑫𝟑𝒅 ; 𝒅𝒛𝟐 > 𝒅𝒙𝒚 , 𝒅𝒙𝟐−𝒚𝟐 > 𝒅𝒙𝒛, 𝒅𝒚𝒛
(c) 𝑫𝟑𝒅 ; 𝒅𝒙𝟐−𝒚𝟐 > 𝒅𝒛𝟐 , 𝒅𝒙𝒚 > 𝒅𝒙𝒛, 𝒅𝒚𝒛
(d) 𝑫𝟑𝒉 ; 𝒅𝒛𝟐> 𝒅𝒙𝟐−𝒚𝟐 , 𝒅𝒙𝒚 > 𝒅𝒙𝒛, 𝒅𝒚𝒛
35
ANSWER KEY
1 C 41 C 81 A 121 A 161 D
2 C 42 A 82 C 122 A 162 C
3 B 43 B 83 A 123 B 163 B
4 A 44 D 84 A 124 B 164 B
5 D 45 A 85 A 125 C 165 A
6 A 46 B 86 C 126 C 166 B
7 D 47 A 87 A 127 B 167 D
8 B 48 A 88 A 128 C 168 B
9 B 49 D 89 C 129 C 169 D
10 C 50 C 90 B 130 C
11 B 51 D 91 B 131 D
12 D 52 B 92 B 132 C
13 C 53 C 93 D 133 B
14 B 54 A 94 B 134 C
15 B 55 A 95 B 135 A
16 B 56 A 96 B 136 A
17 B 57 A 97 D 137 A
18 D 58 A 98 C 138 C
19 C 59 D 99 C 139 B
20 D 60 A 100 D 140 A
21 C 61 A 101 A 141 A
22 C 62 A 102 A 142 C
23 C 63 C 103 A 143 C
24 B 64 A 104 D 144 B
25 C 65 D 105 A 145 C
26 C 66 A 106 C 146 B
27 A 67 C 107 C 147 B
28 C 68 A 108 B 148 B
29 B 69 A 109 B 149 B
30 A 70 C 110 B 150 C
31 C 71 A 111 A 151 C
32 D 72 A 112 A 152 C
33 A 73 A 113 A 153 B
34 A 74 A 114 A 154 D
35 A 75 B 115 A 155 B
36 B 76 D 116 B 156 B
37 A 77 A 117 A 157 C
38 A 78 C 118 A 158 D
39 B 79 A 119 D 159 A
40 C 80 A 120 A 160 B
36
Explanations:
1) c
In, Ni(CN4)2- oxidation state of Ni is +2 & its valence shell electronic configuration is 3d8 .Since CN- is
a strong ligand ,therefore these ligands cause to pair up two unpaired electron ,resulting in vacant 3d
orbital .
Hybridization: dsp2
Geometry: Square planar.
In Ni(Cl4)2-, oxidation state of Ni is +2 & its valence shell electronic configuration is 3d8 Since Cl- is a
weak ligand , no pairing ,none of the 3d orbital is vacant .
Hybridization: sp3
Geometry: tetrahedral
2) c
Oxidation state of Ni is +2 & its valence shell electronic configuration 3d8
For two unpaired electrons geometry is Tetrahedral.
37
3) b
For term symbol only valence shell is considered.
Term symbol 2s+1 Lg/u +/-
S = ½+½ =1 , 2s+1= 3
L= 1x(1)+ 1x(-1) = 0 , the term symbol is ∑
When molecular orbital is π , 2s+1= 3 give negative sign to distinguish ∑ terms
g and u are used for molecules which have COS present , u*u =g
4) a
HOMO= ϭ* of Cr+2 HOMO= ϭ* of Cr+2

+3
LUMO= ϭ* of Co LUMO= π/π* of Ru+3
10
Acceleration =10 Acceleration =102
Inner sphere mechanism is favourable for ϭ→ϭ* transition only.
5) d
For a d5 octahedral complex [Mn(H₂ O)6 ]+2 all transitions are Laporte forbidden (orbital forbidden) as
well as spin forbidden. Absorptions associated with doubly forbidden
transitions are extremely weak, so it is very lightly coloured.
6) a
In the given case ligand in same, so higher the formal oxidation state of the metal , lower will be LMCT.
Mn Oxidation state +7
Cr Oxidation state +6
V Oxidation state +5
So, order is MnO4- < CrO42- < VO43-
7) d
a) Ni+2 = 3d8 , No Jahn - Teller distortion , ideal Oh
b) Mn+2 = 3d5 , No Jahn - Teller distortion , ideal Oh
c) Cr+3= 3d3, No Jahn - Teller distortion , ideal Oh
d) Ti+3= 3d1, shows Jahn - Teller distortion , ideal Oh geometry is not observed
8) b
For 3D
38
2S+1 = 3, 2S=2, S=1

S=1, L=2
For term, S, P, D, F
Value of L= 0, 1, 2, 3
J can have values from [L+S].....[ L-S]
‫׀‬2+1‫׀‬.....‫ ׀‬2-1‫׀‬
3 2 1
Possible J Values are : 3
9) b
Charge transfer spectra are possible due to transfer of electron from ligand to metal or from metal to
ligand.
In Ceric ammonium nitrate (NH4)2 [Ce(NO3)6], metal is in a high oxidation state & ligand has
reducing properties undergo ligand to metal charge transfer.So, Intense colour of Ceric ammonium
nitrate, (NH4)2 [Ce(NO3)6] is due to charge transfer from bidentate NO-3 to Ce+4 which has C.N= 12.
10) c
Kurnakov test is used to distinguish between cisplatin and transplatin, by using thiourea as a reagent.
Cisplatin+ Aqueous thiourea → deep yellow solution and on crystallisation it gives
yellow needle shape crystal of tetrakis(thiourea) platinum
(II) chloride
Transplatin + aqueous thiourea →Colourless solution on crystallisation it gives

white needle shape crystal of trans-bis(thiourea)diaammine
platinum (II) chloride
11) b
Total isomers = geometrical isomer + ½(optical isomer )

Geometrical isomer = 2 isomers ( trans form + cis form)
Optical isomer = 2 isomers ( d –cis-form + l-cis form)
Total isomers= 3
12) d
N→ 1s1 2s2 2p3
L=1+ 0 -1= 0
s=3/2
2s+1=2x3/2+1=4
J=(L+S).... (L-S)
=|0+3/2|.... |0-3/2|= 3/2
Therefore, Ground state term = S
Term symbol = 4S3/2
13) c
[Co(NH3)6]3+ highest value of Δ0
Highest energy (v) or lowest value of wavelength is absorbed
39
14) b
Number of unpaired electrons = 2.
Thus this complex is tetrahedral. Tetrahedral complexes show only one isomer. Magnetic moment
corresponding to two unpaired electrons 2.9 B.M. The hesh values 3.20 due to spin-orbit coupling.
15) b
For allowed transition : a)Spin multiplicity should be same or ΔS = 0
Therefore (a) is not allowed as ΔS ≠ 0
b) ΔL = 0, ± 1 , for allowed transition
Therefore (c) is not allowed as ΔL ≠ 0, ± 1
c) u → g (allowed)
g→ g ( not allowed)
Therefore (b) is correct option.
16) b
For d3 and d8 , the lowest transition gives the value of Δo
17) b
Substitution nucleophilic unimolecular conjugate base mechanism.
40
[CoCl(NH3)5] +2 + OH- →[Co(NH3)4(NH2)Cl] +1 +H2O

_`ab _cde
[Co(NH3)4(NH2)Cl] +1 [Co(NH3) 4(NH2)] +2 + Cl-1
[Co(NH3) 4(NH2)] +2 + OH- → [Co(NH3)5OH] +2
18) d
Explanation
19) c
[Co*(NH3)6]+2→High spin
[Co*(NH3)6]+3 →Low spin
[Ru(NH3)6]+2→ Low spin ;
[Ru*(NH3)6]+3 →Low spin
20) d
For Ce+4 ions NO3- behaves as bidentate ligand. Thus C.N. for [Ce(NO3)6] -2 is 12 and shape
corresponding to C.N=12 is icosahedron.
21) c
Ligand Cl- is both ϭ-donor and π donor
According to LFT, each ligand is always a ϭ -donor some ligands like: NH3 which has only one lone
pair of electrons is only ϭ -donor. Some ligands like F-, Cl-, OH- etc. which hence two or more lone pair
of electrons are ϭ as well as π donors. Some ligands like CO, CN-, SH4, bpy, phen, etc. have π* vacant -
orbitals so these are ϭ -donor but π- acceptors.
22) c
Spin-orbit coupling of d-electrons takes place in which t2g orbitals are unsymmetrically filled.
23) d
Nucleophilic attack on olefins under mild conditions
41
So, it requires activation by coordination to metal.
24) b
For Ni+2 ion in free state, the thus having same spin multiplicity as ³F and ³P. In octahedral field, ³F
splits into 3A2g , 3T2g and 3T1g terms but 3P does not split but it transforms into 3T1g (P). Therefore orgel
diagram is.
Three electronic transitions are 3T2g← 3A2g , 3T1g ←3A2g , 3T1g (P) ←3A2g
25) c
f!
We know that number of microstates=
h!(f$h)!
For d5, r= 5, l=2 Therefore,
n = 2(2l+1)= 2(2x2+1) = 10
ij!
Number of microstates = = 252 = 7×6q
k!×k!
26) c
For allowed transition :
(a) Spin multiplicity should be same or ΔS = 0
A is not allowed transition as ΔS ≠ 0
(b) ΔL = +/-1 , 0 for allowed transition as ΔL ≠ 0, ± 1
therefore E transition not allowed as ΔL ≠ 0, ± 1
B, C, D are allowed .
42
27) a
[Mo2(S₂)6]-2
The structure of [Mo2(S₂)6]-2 cluster is:
So, the bridging Sq$q , is two and co-ordination number of Mo is 8.
28) c
[Co(H2O)6]+2 → t52g e2g
In this electron transition from t52g → e2g , therefore d-d transition.

[CoCl4]-2 → t52g e2g
Electron transfer from e to t2 , therefore d-d transition.
29) b
Total isomers = geometrical isomer + ½(optical isomer)

Geometrical isomer = 2 isomers (trans form + cis form)
Optical isomer = 2 isomers (d –cis-form + l-cis form)
Total isomers= 3
43
30) a
31) c
Electric dipole allowed transition in d2
For electronic transition selection rule, spin multiplicity ∆S=0; ∆l= ±1, ∆J = 0, ±1
3
F→ 3D is allowed transition because ∆S=0, ∆l = -1
32) d
In Be2C3 , Be+ = In tetrahedral voids
C3-2 = In FCC arrangement (Lattice point at corner + at each face centre)

Therefore, coordination number of Be+ = 4
And coordination number of C3-2 = 8
33) a
In trigonal bipyramidal complexes, the two ligands lie on z-axis and the three in xy plane somewhere in
between the axes. In xy plane, there are four electrons and on z-axis there is only one electron in 𝑑t u
orbital
q
Electronic Configuration, 𝑑vt q
= 𝑑wt q
< 𝑑vw , =𝑑vqu $w u <𝑑tqu
34) a
Co3O4 is a normal spinel. In normal spinel the Co+2 ions occupy tetrahedral voids and Co+3 ions occupy
octahedral voids. Therefore, spinel structure of Co3O4 is
(Co+2) t (2CO+3) o O4
35) a
Trans effect of Cl- > NH3
Anti-tumour agent is cis-[Pt(NH3)2CI]
44
The precursor of this complex is [PtCl4]-2
36) b
Explanation
37) a
The rate of water exchange in [Cu(H2O)6] is fastest due to Jahn-Teller distortion. For other three
complexes of 3d-series dipositive metal cation, the rate of water exchange decreases with increase in
effective nuclear charge and decrease in size.
Correct order: (i)> (ii)> (iii)> (iv)
38) a
Trans effect Cl- has larger trans effect than NH3
39) b
45
The electronic transition responsible for the colour of the transition metal ions is dπ →dϭ* which is in
according to LFT.
40) c
The mulliken symbols for the spectroscopic states arising from free ion term F are T₁g +T2g + A2g
41) c
Co(II), Zn(II) and Be(II) form tetrahedral complexes with Cl- or OH-.
Be(II) has no d-orbitals, therefore it form tetrahedral complexes.
Co(II) and Zn(II) form tetrahedral complexes with halides and OH-.
42) a
[CoCl4] 2- +6H2O(blue) ↔ [Co(H2O)6] 2++4Cl-
(blue, tetrahedral) (Light pink, octahedral)
43) b
[Bu4N]2 Re2 Cl8
46
44) d
Among the given ligand CO is most π - acid ligand. Between C2H4 and C2F4 , C2F4 has more tendency
to behave as л-acid ligand due to more electronegative F atoms which holds electron density towards F
atoms and alkene behaves as a better π -аccepting position from metal. NEt3 has very little behaviour
towards л-back bonding. Thus, the order is
NEt3 <C2H4 <C2F4 <CO
45) a
VCl64-
Oh = V+2 = d3
(η5-C5H5)2 Cr
[Co(NO2) 6] 3-
Oh = Co3 = d6 → no unpaired electron.
[Ni(EDTA)] 2-
Ni+2 = d8 → square planar → no unpaired electron.
More unpaired electron in VCl64-
So, it contain highest magnetic moment.
𝜇 = 3 3 + 2 = 15 B.M
47
46) b
Intensity of C 4A 2g→2E g is lowest, since it is spin forbidden.
47) a
As strong field ligand have high crystal field stabilisation energy, according to spec trochemical series of
ligand, the given ligand in order Br- < Cl- < NCS-
Thus, ∆ t of given complexes follow the order: [Co(NCS4)]2- >[Co(Cl4)]2- > [Co(Br4)]2-
48) a
Co2+→ t52g e2g → µ = 3.89BM
Cr2+→ t42g e2g → µ = 4.9BM
Mn2+→ t32g e1g→ µ = 4.9 BM
Fe2+→ t42g e2g→ µ = 4.9BM
49) d
For two non-equivalent π-electrons [π1, π1]
3
ϕ is not possible.
50) c
Order of ligand is spectro chemical series
SCN- < Cl- < F- < CN-
From above it is clear that CN- will produce highest energy difference, followed by F-, Cl-, SCN-. As
colour of complex is complementary colour of absorbed light.
Thus [Co(CN4)]2- absorbs orange colour radiation which complementary colour is blue therefore colour
of [Co(CN4)]2- is blue.
The other combination according to energy are mismatched. Hence, only option (c) is correct.
51) d
Mn → 3d5→ t32g e2g (high spin octahedral)
2+
CFSE in Oh field=(-0.4×3 +0.6×2) =0
Cr+3 →3d3→ t32g e0g (octahedral)
CFSE in octahedral field = -0.4x3∆0= -(0.4x3) ∆o = -1.2∆o

48
52) b
53) c
Pt-S→ dπ-dπ bonding in weaker than that of Pt-P bonding. When Pt-S and Pt-P bond are trans to each
other then Pt-S become weaker therefore in such a situation SCN ligand tends to form bonding through
M atoms of ligand as M do not do not form dπ-pπ bonding. Hence, the most probable structure will be
54) a
Ni2+ is tested by dmg
Ni2+ + 2dmg → [Ni(dmg) 2] (Tschygaeff test )
Red
The structure of complex is
Therefore
Ni-N bonds = 4
Ni-O = 0
Hydrogen bonds = 2
55) a
49
NiBr2 reacts with (Et)(Ph2)P at -78°C in CS2 gives red copound 'A' which on standing at room
temperature turns green to give B.
Measured magnetic moments of 'A' is 0.0 BM ( no unpaired electrons)
and 'B' is 3.2 BM ( two unpaired electrons + orbital contribution)
For A geometry of Ni2+ = 3d8 4s0 = hybridisation = dsp2 (square planar)
For B geometry of Ni2+ = 3d8 4s0 = t62g e2g = two unpaired electrons, hybridisation = sp3 (Tetrahedral)
56) a
In [AgL4]2+ and [AgL6]2+ , Ag2+ has d 9 configuration, hence have unpaired electron. Hence
paramagnetic.
[AgL4] 3+ , Ag3+ has d8 configuration and dsp2 hybridization (square planar so pairing of electron).
Hence, diamagnetic in nature
57) a
[CoL6] 3+ →red colour→ absorbs green radiations
[CoL‫׳‬6] 3+ →green colour→ absorbs red radiations.
Energy of green radiations > energy of red radiations, Therefore, L will be stronger ligand than L'. Thus,
L and L' are NH3 and H2O respectively.
58) a
[V(H2O)6] 3+ →V3+ → 3d2→t2 egº
Two transition
V1= 3T1g (F) → 3T2g (F) ; V2 =3T1g (F) →3T1g (P)
50
59) d
For np2 configurations (microstates)
The configuration (IV) violets the Pauli's Principle, Hence term symbol 3D is not possible.
60) a
In the successor complex inert ruthenium bridged to inert chromium.
61) a
(Phen) is an π-acceptor ligands hence there is mixing of donor and acceptor orbital having similar
symmetry this leads to fast transfer of electron leading to enhance rate of reaction.
[Fe(phen) 3] +3 [Fe(phen) 3] +2
↓ ↓
5 0
t 2g e g t 2g e0g
6
π*5ϭ*0 π*6e0g
Electron transfer takes place from π*6 (Fe+2)→ π*5 (Fe+3)
51
Correct answer is (a)
62) a
s and p both form π -bonding with complex and π-bonding capacity of sulphur is greater than
phosphorus due to smaller size of d-orbital of sulphur. Hence, in presence of sulphur trans to phosphorus
donor atom phosphorus-metal bond will be weak hence they do not lie trans to each other in the
complex. As nitrogen does not involment in π -bonding with complex hence when nitrogen atom is trans
to phosphorus, phosphorus become able to form efficient π -bond with metal hence become stable thats
why P and N are trans to each other
63) c
64) a
52
Terminal NO=1672 cm¹

Bridging NO=1505 cm
65) d
N=1s 2s 2p
L= +1 0 -1
S= 1/2+1/2+1/2=3/2
L=+1+0-1=0
66) a
- -
Trans effect NO2 > Cl > NH3
67) c
Total isomers = geometrical isomer + ½(optical isomer)

Geometrical isomer = 2 isomers (trans form + cis form)
Optical isomer = 2 isomers (d –cis-form + l-cis form)
Total isomers= 3
68) a
Explanation
53
There is spin change during electron transition. Therefore, transition is spin disallowed
69) a
[CoCl(NH3)5]+2 + OH- → [Co(NH3)4(NH2)Cl]+1 +H2O
[Co(NH3)4(NH2)Cl]+1 → [Co(NH3) 4(NH2)]+2 + Cl-1
[Co(NH3) 4(NH2)]+2 + OH- → [Co(NH3)5OH]+2
Base hydrolysis of [CoCl(NH3)5]+2 depends on the concentration of both [CoCl(NH3)5]+2

and base. In this reaction OH- abstract proton from coordinated NH3.
The base hydrolysis of [Co(CN)]-3 is independent of base because it has no ionizable proton.
70) c
[Ne] 2p1 3p1
2s+1=3; 2s=2; s=1
For, D, L=2
J=|L+s|..... |L-s|=|2+1|... |2-1|= 3,2,1
Levels for 3D are 3D3 , 3D2 , 3D1
71) a
[MnF6] -3 , Mn+3→3d4 → 𝒕𝟑𝟐𝒈 𝒆𝟏𝒈
(HS)
𝜇 = 4 4 + 2 = 24 = 4.9
S =2 →2s+1 = 2×2+1=5
L=2→D
Ground state term symbol ³D
72) a
54
It is first inorganic optically active compound discovered by Werner.
Number of Co-O bonds = 12

Number of Co-N bonds 12
73) a
[CrCl6] -3
Cr 3+ →3d3
𝜇 s = 𝑛(𝑛 + 2) = 3(3 + 2) = 3.87
𝜇 L+S = 𝑛 𝑛 + 2 + 𝑙(𝑙 + 1) BM
𝜇 L+S = 𝑛 𝑛 + 2 + 𝑙(𝑙 + 1) = 3 3 + 2 + 3(3 + 1) = 15 + 12 = 27 = 5.20 BM
74) a
The bonding in phosphine ligands, like that of carbonyls having two components. The primary
component is sigma donation of the phosphine lone pain to on empty orbital on the metal. The second
component is back donation from filled metal orbital to an empty orbital on the phosphine ligand. This
empty phosphorous orbital has been described as being either a d-orbital or an antibonding sigma orbital
(ϭ*).
55
So, in transition metal phosphine (M-PR3) complexes, the back bonding involves donation of electrons
from M(t2g )→ PR3(σ*)
75) b
Option c and d (incorrect) as ΔS ≠ 0
b) ΔL = ±1 , for allowed transition
3S→3P
ΔS = 3-3=0
ΔL= 1-0= 1
76) d
ns1 np1
L=1 ≡ 𝑃
S=1 hence, 2S+1=3
For J value, if orbital is less than half filled than
J=|L-S|=|1-1|=0
Hence, 3P0
77) a
Fe(II) protoporphyrin → π →π* transition
[Mn(H₂O) 6]Cl₂ → Mn+2→d5 (high spin) spin forbidden (d-d) transition.
56
∆S=1. Hence, not allowed.
[Co(H₂O)6]Cl2 →Co+2→ d7 (high spin) (d-d)
∆S= 0. hence allowed
78) c
K4[Cr(CN) 6]= Cr+2→ d4 (low spin)
For a compound to show John Teller Distortion eg or t2g set should be electronically degenerate.
(1) Cr+2 → d4 (low spin)
Electronically degenerate hence show John Teller Distortion.
(2) K4[Fe(CN) 6] = Fe+2 (low spin) = d6 (low spin)
Electronically non-degenerate hence, no Jahn-Teller distrotion
(3) K3[Co(CN)6] = Co+3 → d6 (low spin)

57
Same as above hence, no Jahn-Teller Distrotion.
(4) K4[Mn(CN) 6] = Mn+2 (low spin)
electronically degenerate
Hence, complex will show Jahn-Teller Distortion.
79) a
[Fe(Phen) 2 (NCS) 2]
Fe+2 = d6 complex
At high temperature high spin and at low temperature low spin behaviour at 250 K
CFSE = 1.6 Δ0 +1.2 Δ0 =0.44,

𝜇 = 𝑛(𝑛 + 2) = 4(4 + 2) = 4.90 at 150 K

CFSE -0.4 x 6 Δ0 = -2.4∆
𝜇 =0
80) a
Taking the valence shell configuration
Be 2s1 3s1
s=1/2+1/2 =1
Multiplicity =2S+1= 2x1+1=3
L= 0+0= 0 , S term
J= (L+S) = (0+1) = 1
Hence, terms is 3S1
58
81) a
[CrO4]2-< [MnO4]2- < [FeO4]2-
All have +6 oxidation state but due to smaller size on going from Cr to Fe, Fe has very high charge
density. Hence, it has very high tendency to accept electron. Hence, strongest oxidising agent.
82) c
Number of unpaired electrons
(A) [CoF6] 3- → d6 (high spin) = t42g e2g 4
(B) [IrCl6] 3- →d6 (low spin) = t62g e0g 0
(C) [Fe(H2O) 6] 2+ →d6 (high spin) = t42g e2g 4
Since, A and C has same number of unpaired electron. Hence, they have same magnetic moment. As A
and Care 3d-block metal with weak ligand. Hence, they are high spin while Ir being 5d-metal is low
spin. Because 5d has greater splitting power than 3d.
83) a
[Mn (H2O) 6] 2+ = d6 (HS)
As all the levels are electronically non-degenerate. Hence, No Jahn-Teller distortion. Therefore, all the
Mn-O bond length will be equal.
84) a
[Fe(phen) 3] 2+ → [Fe(phen) 3] 3+ + e-
( Red) (Blue)
In presence of oxidising agent like K2Cr2O7 , [Fe(phen) 3] 2+ changes it colours from red to blue hence,
they are used in redox titration.
85) a
The stability (formation constant for complexation of cryptate complex depends upon)
(1) size of cavity
(2) size of metal cation
59
Hence, K+ ion will form most stable complex with cryptand-222.
86) c
E2 > E1 hence, energy required for transfer of electron from oxygen to Re falls in UV region. Hence,
[ReO4] - colourless while in [MnO4] - due to less energy difference it falls in visible region. Hence,
[MnO4] - coloured. Also as both Mn and Fe have +7 oxidation state i.e. they have no d-electron hence,
no d-d transition and colour arises due to LMCT.
87) a
[Co(CN) 5Cl] 3- + OH- →[Co(CN)5(OH)] 3- +Cl-
The reaction proceed through dissociative pathway and rate is dependent only concentration of
substrates. As substate do not have acidic hydrogen. Hence, it does not undergo SN 1CB mechanism.
[Co(CN) 5Cl] 3- → [Co(CN) 5] 2- + OH- → [Co(CN) 5OH] 3-
(slow)
88) a
Explanation
60
89) c
Tanabe-Sugano are useful in interpretation of spectra of both high spin and low spin complexes of d2-
d8 metal cation.
In Tanabe-Sugano, the energy of excited sate (expressed as E/B) are plotted against ligand field strength
(expressed as (∆0 /B).
Zero energy is taken for the lowest term and also two form of same symmetry never cross each other
and they bent for apart from each other due to repulsion.
90) b
[CrF6] -3 = d3
Orgel diagram for d3.
61
ground state= 4F
First excited state = 4P
4
A2g →4T2g (Δ0)
v1 = 14900 cm-1 ; v2 = 22700 cm-1 ; v3 = 34400 cm-1

Since, 4T1g (P) and 4T1g (F) have no fix energy therefore, they will not provide accurate value of Δ0.
Thus, energy difference between 4A2g → 4T2g 14900 cm-1 will be correspond to Δ0
91) b
For [1s22s2p6 3p1]
i
2s+1=2× + 1 = 2
q
J=|l+s|..... |l-s|
=|1+½|.....|1-½|
= 3/2 1/2
Term symbol 2P3/2 2
P1/2
92) b
3
F→ 3D
Since, for allowed transition (atomic), ∆S=0, ∆L=0,±1
In option a and c spin multiplicity is not same therefore incorrect
In option d , ∆L=2 therefore incorrect.
93) d
[NiIIL6] n+ or n- has shows absorption bands at 8500, 15400, and 26000 cm-1
[NiII Lʹ6] n+ or n- at 10750, 17500 and 28200 cm-1
62
as for first complex absorptions bands are at low energy i.e. it has weak splitting therefore, it has weak
ligand and for II complex high energy absorption bands corresponds to strong ligand.Thus, L is weak
and L' is strong ligand.
94) b
Number of microstate in 3F is calculated as (2S + 1) (2L+1)
For F, L=3.
Hence, (3) (2x3+1) =21
95) b
Chelate effect is predominately due to entropy change
∆H nearly same but entropy change is more.
96) b
D6 =
L= ∑ML = 5-3 = 2 = D
S=2 , 2S+1=5
Hence, lowest energy form = 5D
97) d
H2 (excited state)
L=0=Σ
S=1/2+1/2= 1 , 2s+1=3
gxu=u = 3∑. 𝒖
For half filled.
98) c
[Cr(bipyridyl)3]+3→ d3 = 4F (ground state term)
As phosphorescence is spin-forbidden transition and also occurs when electron comes from excited to
ground state. Hence, transition 4A2g ← 2Eg is responsible for the phosphorescence.
99) c
For orbital contribution the set should be unsymmetrically filled
[Cu(H2O)6]+2→ t62g e3g →No contribution
[Ni(H2O)6]+2→ t62g e2g →No contribution
63
[Co(H2O)6]+2→ t52g e2g → Orbital contribution

[Cr(H2O)6]+2→ t32g e1g → No contribution
100) d
In KMnO4 all the electrons are paired. However, its paramagnetic susceptibility of the order of 10-6 cm3
mol-1 is due to the temperature independent paramagnetism.
101) a
The complexes having T ground state have orbital contribution to magnetic moment however for
complex having A or E ground state some time µeff is slightly greater than µspin is due to mixing of first
excited state T (having same spin multiplicity to ground state) mixes with A or E due to spin coupling
and there is calculated by
𝝀𝜶
µeff = µs 𝟏 −
𝚫
𝝀𝜶
Hence, higher value of µeff = µs 𝟏 −
𝚫
102) a
In halogen molecules, the π*→ ϭ*transitions are responsible for their colours as evident from the
following figure
103) a
The-donor ligands such as Cl-, Br-, I-, N-bonded NCS- etc stabilize the TBP intermediate and favour the
stereochemical change. The trans-forms tendency to isomerise in the order
A = NO2- <Cl- < NCS- <OH
104) d
According to Nephelauxetic series
F- > H2O > NH3 > en > NCS- > Cl CN- > Br-
The highest value of is for F-
64
105) a
The Eg ← A2g transition in the electronic spectrum of [Cr(NH3)6]+3 occurs nearly at 650 nm.
2 4
106) c
[Cr(NH3)6]+3
Ce+4 → 4f0 → No f-f Transition
No unpaired electrons.
It is diamagnetic and its colour is due to LMCT. Its C.N. = 10
107) c
-4
[FeO4] → Jahn-Teller distorted away from the ideal tetrahedral towards a flatterred structure
it is paramagnetic due to unpaired electron D2d symmetry
108) b
[Mn(H2O6)]+2 → H2O is a weak ligand, No pairing occurs.
S=5/2 , 2S+1=6
L=0→ S Term
Ground state term → 6S
Cr+3 =
L= 3→F Term
S= 3/2 ; 2S+1=2x3/2+1=4
Ground state term→ 4F
Cu+2 = d9
L= ∑ML = 2 →D
S=1/2 , 2S+1=2
Ground state term → 2D
109) b
[CoCl(NH3)5] + OH- →[Co(NH3)4(NH2)Cl] +1 +H2O
+2
‡ˆ‰Š ‡‹Œ•
[Co(NH3) 4(NH2)] +2 +OH- → [Co(NH3)5OH] +2
110) b
𝑘 12 = 𝑘 11 𝐾𝑘 22 𝑓 = 5×4×10‘ ×2×10’ ×1.0 = 20×10k = 2.0×10“
111) a
65
Fischer carbene carbon is electrophilic in nature due to strong π- acceptor ligands
112) a
The arrangements for [ 1πg ]1 [3ϭu]1configurations are
S= 1, 2S+1=3
L=1→ πTerm
Spectroscopic Term = 3π
L=1→ πTerm
S=0, 2S+1= 1
Spectroscopic Term → 1S
Thus one of possible moleculer term symbol is 1π
113) a
In CdS, HgS and BiI3 colour is due to LMCT as Cd+2 and Hg+2 has d10 configuration. Hence, no d-d
transition. Also, no MLCT as ligand is not π -acceptor.
114) a
Change in CFSE on going for Oh to five coordinate intermediate for ions is as follows.
V+2 (d3) = -2.00
Cr+3 (d3) = -2.00
Ni+2 (d8) = -2.00
115) a
NR → Dithiocarbamate
OR → Xanthate
O- → Dithiocarbonate
SR → Thioxanthate
116) b
”•
µeff = µs 1 −
–
i i ijš›
Δ = = $—
×10 cm = cm-1
” “qk “qk
66
For Cu+2 → Term is 2D , hence, α = 2 , λ =-625 cm-1

q× $“qk ×“qk q×“qk ×“qk
µeff = 1.73 1 − ›
= 1.73 1 + ›
ij ij
q×“qk ×“qk
1.73 1 + = 1.73{1+ 0.078} = 1.73{1.078} = 1.864
ij›
µeff = 1.864
117) a
As the strength of ligand increases energy for d-d transition increases.
Strength of ligand order is F- < ox-2 < en. Option A is correct .
All complex have same number of unpaired electron. Hence, all have same spin only magnetic moment.
Option B is correct .
[Cr(ox)3]-3 and [Cr(en)3]+3 will show optical isomer. As t2g level is electronically non-degenerate.
Hence, there will be no Jahn-Teller distortion. Option D is incorrect .
118) a
Thus, order for energy absorption is 675 (A) < 615 (B) < 565 (C)
Δ0 increases as the ligand field strength increases H2O < NH3 < en
Complementary colour of blue → Orange , green →Red, Violet → Yellow
Energy order for absorbed light is yellow > orange > red
Thus, A absorbs red hence it is green
B absorbs orange hence it is blue
C absorbs yellow hence it is violet
119) d
(A) [TiF6]-3
Ti ⇒ 3d2 4s2
Ti+3⇒ 3d1 4s0
(B) [CrF6]-3
Cr = 3d5 4s1
Cr+3 = 3d3 4s0
67
(C) [MnF6]-3
Mn = 3d5 4s2
Mn+3 =3d4
(D) [CoF6]-3
Co=3d7 4s2
Co-3 =3d6 4s0
Hence, A<B<C≈ D
120) a
K2CuF6 = 3K [CuF6]-3 oxidation state of Cu+3 = 3d8
+
Thus, Cu+3 (Oh) ,d8

KCuL2 oxidation state of Cu = 1 + x - 4 = 0 => x=+3
Cu+3 (d8)
Hence, square planar low spin
121) a
Mechanism of base hydrolysis can be given as
[CoCl(NH3)5] +2 + OH- →[Co(NH3)4(NH2)Cl] +1 +H2O
68
_`ab _cde
[Co(NH3) 4(NH2)] +2 +OH- → [Co(NH3)5OH] +2
122) a
Small P-Pd-P angle , less steric hindrance effective π Pd-SCN- bonding
Increase in P-Pd-P angle , increase in steric hindrance . No, effective π bonding from the P atom , the S
atom of SCN- ligand can form π bond but due to steric hindrance SCN- binds through N atom.
P-Pd-P angle , further increase with increase in size of chelate ring and hence steric hindrance increases .
No effective , π bonding from the P atom , the S atom of SCN- ligand can form π bond but steric
hindrance favours the Pd- N bonding .
123) b
For d (high spin) there is one spin allowed transition from 5T2g → 5Eg
6
In case of d6 low spin commonly two spin allowed transitions are observed.
1
A1g → 1T1g
1
A1g→ 1T2g
there are additional spin allowed transitions at higher energy but they are marked by allowed transitions.
Hence, are not observed
124) b
69
In I3- there is interaction between ϭ* a of I2 and non-bonding electron of I-. In case propanone and Br2
there in interaction between ϭ* of Br2 and non-bonding electron of propanone. Thus, both I2 and Br2
behave as acid.
125) c
Spin-orbit coupling is larger for the heavier atoms (Inner transition) and very small for lighter atoms.
126) c
Co (high spin) → 3d7 4s0
+3
S=1/2+1/2+1/2=3/2
L=4+2-0-1-2
L=3
Degeneracy for d-orbital = (2S+1)(2L+1)=(2x3/2+1)(2x3+1)=4×7=28
127) b
High value (4.1 B.M.) is due to µspin+ orbital contribution because t2 is electronically degenerate
128) c
-2
CrO4
Cr+6 → 3d0 4s0
O-2 →2s22p6
MoO4-2
Mo+6 → 4d0 5s0
70
In both Cr+6 and Mo+6 ions, there is no d-electrons, therefore, there is no d-d transition, since in both the
ions. oxidation state is very high, there is LMCT in both cases. The energy gap between 2p6 (O-2) and
3d0 (Cr+6) is less than that between 2p6 (O-2) and 4d0 (Mo+6). Thus, LMCT energy
in CrO4-2 is less (high λmax) than that of MoO4-2 (low λmax).
129) c
S=1/2+1/2=1
2S+1= 2x1+1=3
J=|l+s|...|l - s| = |1+0|...|1-0| =1
l=0 → S (term)
3
S1
130) c
Electronic configuration of Cr =3d 4s
Electronic configuration of Cr+2 = 3d4
Electronic configuration of V+2 =3d3
(A) Because of high nuclear charge of Cr is greater than that of V, Cr has higher. This ionization energy
than V. Hence, Cr+2 is not easier to oxidized than V+2 in gas phase. Thus, option (a) is incorrect.
(B) Cr+2 (aq) →[Cr(H2O)6 ] +2 →[Cr(H2O)6]+3 +e-
Less stable More stable

As less CFSE As more CFSE
V+2 (aq) →[V(H2O)6]+2 →[V(H2O)6]+3 + e-
Thus, V+2 (aq) does not easily oxidized
Thus, Cr+2 (aq) is more powerful reducing agent than V+2 (aq)
(C) Cr+2 (aq) is more labile than V+2 (aq). Also, Cr+2 belongs to class1 metals and V+2 belongs to class 3
metals, Thus, the rate of water exchange in Cr+2 (aq)faster than V+2 (aq)
131) d
(I) [Fe(CN)6]-3 + [Co(CN)5]-3 → [(NC)5Fe-CN-Co(CN)5]-6
electron transfer
[Fe(CN)6]-4 + [Co(CN)5(OH2)]-2
(Inner sphere mechanism)
71
(II) [Co(bipy)3]+2 + [Co(bipy)3]+3 → [Co(bipy)3]+3 +[Co(bipy)3]+2

(outer sphere mechanism)
- H2O electron transfer
(III) [Co(NH3)F]+2 + [Cr(H2O)6]+2 [(H3N)5CoIII-F-CrII(OH2)5]+4
+ H2O
[(H3N)5CoII-F-CrIII(OH2)5]+4 [Co (NH3)5(OH)2]+2 + [Cr(OH2)5F]+2
(Inner sphere mechanism)
Marcus equation is applicable only for cross-outer sphere reactions.
(B) is a self exchange reaction, its rate of electron transfer can be calculated experimentally.
No need to apply marcus equation.
(Reference basic inorganic chemistry by F.Albert Cotton, G Wilkinson and Paul L.Galls) third eddition.
In this question only (d) statement is correct.
132) c
b) ΔL = 0, ± 1 , for allowed transition
Therefore (4) is not allowed as ΔL ≠ 0, ± 1
c) u → g (allowed)
g→ g ( not allowed)
Therefore (1, 2) are not allowed
[+ → -] → forbidden so, therefore (1, 2) are not allowed
[+ → +] → allowed
133) b
NO, I2- , Cu+2 and VO+2 is paramagnetic. Hence, EPR active where as I2 is diamagnetic and EPR
inactive.
134) c
[Co(NCS)(NH3)5]+2 +[Fe(H2O)6]+2 [(HN)5Co –SCN-Fe(H2O)5]+4
H2O
[(HN)5Co-SCN-Fe(H2O)5]+4 [Fe(SCN)(H2O)5]+2 +[Co(NH3)5(H2O)]+2
Intermediate
+5H3O+
[Co(NH3)5(H2O)]+2 [Co(H2O)5]+2 +5NH4+
[Fe(SCN)(H2O)5] +H2O → [Fe(H2O)6]+3 +SCN-
+2
Intermediate
135) a
136) a
72
For strong Jahn-Teller distortion eg orbital must be assymetrical filled.

t62g e1g , t32g e1g , t62g e3g
137) a
The correct order of intensity of d-d transitions in the complexes follows order
cis-[M(H2O)4Cl2] > trans-[M(H₂O)4Cl2] > [M(H₂O)6]+2
138) c
A react faster than B and B result in a mixture of product
139) b
As the oxidation state increases and size of central decreases ligand exchange rate decreases.
140) a
Electron transfer reactions by self-exchange electron transfer is fast when HOMO is π* and LUMO is
also π* i.e. electron transfer is from a π*of reductant to the π* of oxidant.
(a) [Ru(NH3)6]+2 + [Ru(NH3)6]+3 → [Ru(NH3)6]+3 + [Ru(NH3)6]+2 [ Reaction is fast]
6 0
(π*) (ϭ*) (π*)5(ϭ*)0
6
HOMO=(π*) LUMO=(π*)5
(b) [Co(NH3)6]+2 +[Co(NH3)6]+3 → [Co(NH3)6]+3 +[Co(NH3)6]+2 [Reaction is slow]
(π*)5(ϭ*)2 (π*)6(ϭ*)0
HOMO=(π*)5 LUMO=( ϭ*)0
(c) [Cr(H2O)6] + [Cr(H2O)6]+3 → [Cr(H2O)6]+3 + [Cr(H2O)6]+2 [Reaction is slow]
+2
(π*)3(ϭ*)1 (π*)3(ϭ*)0
1
HOMO=( ϭ*) LUMO=( ϭ*)0
(d) [Fe(H2O)6]+2 +[Fe(H2O)6]+3 → [Fe(H2O)6]+3 + [Fe(H2O)6]+2 [Reaction is fast]
73
(π*)4(ϭ*)2 (π*)3(ϭ*)0
4
HOMO=(π*) LUMO=( π*)3
Both reactions (a) and (d) are fast but reaction (a) is much faster than (d) because there is small change
in M-L bond length in reaction (a) i.e. less activation energy is required
141) a
Hg (aq) + X (aq) → [HgX]+ (aq)
+2 -
The stability constants for [HgX]+ (aq) for X= F, Cl , Br follow the order: F < Cl < Br .Because Hg+2 is
soft acid and Br- is soft base.
142) c
[Mn(H2O)6]+2 → t2g3 eg2 : High spin complex
In this complex, there is neither orbital contribution nor temperature independent paramagnetism (No L-
S coupling) and α =0. Thus, µobserved = µspin
[Co(H2O)6]+3 is a low spin complex.
Co+3 → d6 ie. t2g6 eg0
No unpaired electron.
Therefore, it is diamagnetic in nature.
143) c
Ti →d complex: t2g1 eg0
+3 1
Ti+3 complex exhibit one broad band due to

(i) Vibronic coupling
(ii) Jahn-Teller distortion
(iii) Spin-orbit coupling
Co+2 → d7 complex
Exhibit three broad bands due to following transitions:
4
T1g →4T2g ; 4T1g → 4A2g ; 4T1g → 4 T1g(P)
•Cr+3 →d3 complex
Exhibit three broad bands due to following transitions:
4
A2g →4T2g ; 4A2g → 4T1g(F) ; 4A2g → 4 T1g(P)
•Mn2+ complex→ d5 complex exhibit a series of very weak (spin forbidden, Laporte forbidden and sharp
bands).
•Ni+2 →d8 exhibit three broad bands due to following transitions:
3
A2g → 3T2g ; 3A2g → 3T1g (F); 3A2g → 3 T1g(P)
144) b
trans-[CoLCl(en)2]+ → A (on hydrolysis)
L= NO2-, NCS-, OH- ,Cl-
The tendency to form cis-isomer of the product (A) follows the order:
L= NO2- < Cl- < NCS- < OH-
74
145) c
Ir = 9e-
PPh3= 2e- each
CO= 2e-
NO (bent) = 1e- (lets consider)
9e- + 4e- + 2e- + 1e- +1e- -1e- = 16e-
Considering NO in bent form gives TVE = 16, thus a square pyramidal structure of complex gains
stability with 16 e-, So we can say NO present in bent mode
Ru= 8 e-
PPh3=2 e- each
Cl= 1 e-
NO(bent) = 1 e-
NO(linear) = 3 e-
8e- + 4e- + 1e- + 1e- +3e- -1e- = 16e-
Considering one NO in bent form and another in linear gives TVE = 16, thus a square pyramidal
structure of complex gains stability with 16 e-, So we can say One NO preset in bent mode and other
in linear mode .
Co = 9 e-
AsR3=2 e- each
NCS=1 e-
NO(bent)=1 e-
75
9e- + 8e- + 1e- + 1e- -1e- = 18e-

Considering NO in bent form gives TVE = 18, thus an octahedral structure of complex gains stability
with 18e-, So we can say NO present in bent mode
Cr=6 e-
CN= 1 e- (each)
NO(linear) = 3 e-
6e- + 5e- + 3e- + 3e- = 17e-

Considering NO in linear form gives TVE = 17, thus an octahedral structure of complex gains stability
with 18e-, So we can say NO present in linear form (17e- species is considered quite stable as on
putting NO as bent, we were just getting 15e-, which would be too unstable)
146) b
An aqueous solution of Fe(III) ion (A) gives a blood-red colour on reaction with KSCN the blood red
colour is due to formation of [Fe(SCN)(H2O)5]+2 (B). The colour may also used for the identification of
Iron (III). This colour is destroyed by the addition of F- ion due to the formation of [FeF6]-3 (C).
NaF
[Fe(H2O)6]+3 + SCN- → [Fe(SCN)(H2O)5]+2 [FeF6]-3
(A) (B) (C)
Blood red colour colourles , d-d transition ,laporte
Due to LMCT forbidden ,spin forbidden
147) b
In chlorophyll, visible absorption band arise from excitation of electron from the π-HOMO to π*
LUMO, thus, has maximum value of molar extinction coefficient value.
[NiCl4]-2 is a tetrahedral comples, thus, p-d mixing will be there, hence, Laporte partially allowed and
spin allowed transition.
In [Cr(H2O)6]+2 , d-d transition will be there. hence, Laporte forbidden and spin allowed transition.
In [Mn(H2O)6]+2 transition is both Laporte and spin forbidden.
So, the order of molar extinction coefficient value is:
Chlorophyll > [NiCl4]-2 > [Cr(H2O)6]+2 > [Mn(H2O)6]+2
148) b
The base hydrolysis of [Co(py)4Cl2]+ is independent OH- of concentration because there is no protonic
hydrogen in the complex.
149) b
76
FeCr2O4 has normal spinel structure thus, Fe+2 occupy tetrahedral site. NiGa2O4 has inverse spinel
structure thus, Ni+2 occupy octahedral site.
150) c
cis-[Fe(phen)2 (NCS-N)2] (A) complex at high temperature (300K) exists as high spin with four
unpaired electrons but when temperature is decreased, there is sharp decrease in magnetic moment at
174 K and complex becomes low spin. This indicates that at 174K, complex (A) exists as both high spin
and low spin.
Thus, at 300K, complex A has four unpaired electrons.
u
µ = u 𝑛(𝑛 + 2) = u 4(6) = 24 = 4.89 BM
Complex [Fe(phen)3]Cl2 (B) at 300K is a low spin complex, thus have t2g6 eg0 configuration ,hence no
unpaired electron.
µ = u 𝑛(𝑛 + 2) = u 0(0 + 2) = 0 BM
151) c
In [IrBr6] oxidation state of Ir is +4 and Ir+4 is low spin. octahedral complex with the electronic
-2
configuration:
There are two charge transfer bands and their origin are ligand→ metal (ϭ →t2g and ϭ →eg )
as shown in the figure.
Other transitions are of high energy and do not observed.
152) c
+2
[*Co(NH3)6] + [Co(NH3)6]+3 → [*Co(NH3)6]+3 + [Co(NH3)6]+2
High spin low spin
t2g5 eg2 t2g 6 eg0
77
Labile Inert
Co- NH3 Co- NH3 Bond length = 193.6pm
Bond length = 211.4pm
The rate of electron transfer for the reaction is very slow (second order rate constant =10-6 L mol-1s-1)
because of following reason :
• Low spin [Co(NH3)6]+3 (configuration t2g 6 eg0) has all the metal -electrons pointing in between the
ligands whereas, high spin [*Co(NH3)6]+2 (configuration t2g5 eg2 ) has two eg electrons pointing directly
at the ligands. The electrons present in eg orbitals cause more repulsion with ligands than that of t2g
electrons. Thus, M-L bond lengths in both complexes are different enough and more activation energy is
needed to make them the same in transition state .
Also, no simple addition or removal of an electron can convert these configuration into one another.
Thus, it is necessary to excite the oxidation states before the reaction can occur, as shown below:
‹q© to t2g
*Co+2 (t2g5 eg2) → (t2g6 eg1) (t2g5 eg1) → (t2g6 eg0) *Co+3
(electronic transition)
‹q© to t2g
Co+3 (t2g6 eg0) → (t2g5 eg1) (t2g6 eg1) → (t2g5 eg2) Co+2
(electronic transition)
153) b
Geometrical isomers for complex [RhH (C≡CR)2(PMe3)3] are
154) d
Solutions of I2, in donor solvents such as pyridine, ethers, ketones, alcohol are brown or yellow due to
formation of a charge transfer complex. Acetone or ethanol and similar compounds donate electron
density through a ϭ lone pair to the ϭ* -orbital of iodine.
155) b
In the complexes, [Fe(bpy)3]+2, [Ru(bpy)3]+2 and [Fe(phen)3]+2 , ligands bpy and phen have empty π*
orbitals, thus, band in electronic spectra is due to metal to ligand charge transfer (MLCT). Whereas, the
other complexes i.e. [FeCl4]2- (220 nm), [FeBr4]2- (244 nm), [ReO4]- (227 nm) and [TcO4]- (286 nm)
show LMCT bands.
156) b
3
d -electronic configuration:
L=2+1+0 = 3 i.e. ‘F’

S= 3 x 1/2 = 3/2
2S+1 = 2 x 3/2 + 1 = 4
78
J = less than half filled= L-S= 3-3/2 = 3/2

Thus, ground state term is = 2S+1LJ = 4F3/2
157) c
[CoIII(NH3)5Cl]+2 + [CrII(OH2)6]+2 [(NH3)5CoIII –Cl–CrII(H2O)5]+4
Inert Labile
↓
[(NH3)5CoII –Cl–CrIII(H2O)5]+4
Labile Inert
↓
[Co(NH3)5]+2 + [Co(H2O)5Cl]+2
(B)
+5H3O+
[Co(NH3)5]+2 +H2O → [Co(NH3)5(H2O)]+2 [Co(H2O)6]+2 +5NH4+
158) d
In [Cr(en)3]+3 , which is an octahedral complex, three spin allowed electronic transitions are
observed.
Trans-[Cr(en)2F2]+ is a tetragonal complex. Therefore, there is splitting of 4T2g , 4T1g, and 4T1g (P) states.
4
A2g term does not split. Thus, 6 electronic transitions are observed.
159) a
The value of magnetic moment will be independent of temperature for [Fe(acac)3] because this complex
is high spin with electronic configuration and the promotion of electron from t2g to eg or eg to t2g is spin
forbidden with variation of temperature. Also, the high spin [Fe(acac)3] has ground state 6A1g and it has
no excited states of the same spin multiplicity as that of the ground state.
79
160) b
Solid Thiourea
KNO2 in dil . AcOH N2 gas ↑ + SCN- + H2O
(P) ↓ dil FeCl3
[Hg(SCN)4]2- °±`²cdd HgCl2
[Fe(H2O)5(SCN)]2+
solution
Colourless (R) Blood red (Q)
161) d
+
N2 = ϭ 1s ϭ 1s* ϭ22s ϭ22s* π22px = π22py ϭ12pz
2 2
ϭ12pz = gerade
Ʌ = 0 i.e. Σ
S=½
2S+1 = 2 × 1/2 + 1 = 2
As ϭ12pz orbital is symmetric, (+) is used.
Thus, term symbol of N2+, is Ʌ. 2 .
g/u = ∑¸
162) c
In the formation of NaCl2 a very large second stage ionization energy is required as Na+ already attain
nearest noble gas configuration thus, the calculated heat of formation (∆Hf) will be positive due to high
value of I.E2 of Na.
Ca shows +2 as stable oxidation state but it can release only a single electron easily (though it is less
stable than Ca+2). Thus, the calculated heat of formation (∆Hf) will be negative for CaF.
163) Correct option (b)

Steric hindrance favours dissociative substitution in octahedral complexes, hence statement (1) is correct
Higher charge on metal will not allow dissociation of existing ligand and will not favour acceptance of
electron pair of entering ligands, hence statement (2) is incorrect
During dissociative substitution reaction a penta coordinated intermediate is observed, hence statement
(3) is also correct.
Nature of entering ligand does not influence the reaction much, hence statement (4) is incorrect.
164.) Correct option (b)

80
165.) Correct option (a)

Oxidation state of metals in 𝑉𝑂»‘$ , 𝐶𝑟𝑂»q$ and 𝑀𝑛𝑂»$ are V(+5), Cr(+6) and Mn(+7) respectively,
Since, 𝜆ÀÁÂÃ ∝ 𝑂𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛 𝑆𝑡𝑎𝑡𝑒 𝑜𝑓 𝑚𝑒𝑡𝑎𝑙
Thus preferred order will be, 𝑉𝑂»‘$ < 𝐶𝑟𝑂»q$ < 𝑀𝑛𝑂»$
As 𝜆ÀÁÂÃ decreases on going down the group,

thus preferred order will be 𝑊𝑂»q$ < 𝑀𝑜𝑂»q$ < 𝐶𝑟𝑂»q$

Electron transfer between Cr+2(d4 system) and Cr+3(d3 system) takes place via Inner Sphere electron
transfer mechanism, as Cr+2 is Labile complex having bridging ligand (H2O).
electron transfer takes place between HOMO of Cr+2 (eg considered as σ*) to LUMO of Cr+3 (eg
considered as σ*), thus electron transfer is from σ*⟶ σ*. Hence statement A is correct.
Statement B is correct as it involves large inner-sphere reorganization energy.
Statement C is incorrect as M–L bond lengths changes while inner-sphere electron transfer mechanism.
Rate of self-exchange electron transfer is always slow than cross-exchange electron transfer mechanism.

167.) option (d)
Correct
81
SHORT TRICK:
1. When point group is C3V then number of IR bands will be N-1, where N is number of CO
ligands
2. When point group is C2V then number of IR bands will be N, where N is number of CO
ligands
Ground State term symbol will be

𝑚` = + 2 + 1 + 0 = 3 , thus term will be F
‘
spin multiplicity = 2𝑆 + 1 = 2× + 1 = 4
q
Thus overall ground state term = 4F
Now, according to Orgel diagram for d3 system
82
169.) Correct option (d)

Point Group of Trigonal bipyramidal geometry is D3h, as it has C3 principle axis of rotation and 3C2 axes
perpendicular to principle axis, also there is a horizontal plane.
The order of energies of d-orbitals for TBP geometry will be 𝒅𝒛𝟐> 𝒅𝒙𝟐−𝒚𝟐 , 𝒅𝒙𝒚 > 𝒅𝒙𝒛, 𝒅𝒚𝒛
1

84
Organometallic Compounds
CSIR JUNE 2011

1.The oxidative addition and reductive elimination steps are favoured by
(a) Electron rich metal centres. (b) Electron deficient metal centers
(c) Electron deficient and electron rich metal centers respectively.
(d) Electron rich and electron deficient metal centers respectively
2. Identify the order according to increasing stability of the following organometallic TiMe4 ,
Ti(CH2Ph)4, Ti(i-Pr)4, and TiEt4
(Me= methyl, Ph=phenyl, i-Pr=isopropyl, Et = ethyl)
(a) Ti(Ch2Ph) 4 <Ti(i-pr) 4 <TiEt4 < TiMe4
(b) TiEt4 <TiMe4 <Ti(i-Pr) 4 <Ti(CH2Ph)4
(c) Ti(i-Pr)4 <TiEt4 <TiMe4 <Ti(CH2Ph)4
(d) TiMe4 < TiEt4 <Ti(i-Pr) 4 <Ti(CH2Ph)4
Q3. Oxidation occurs very easily in case of

(a) (η5-C5H5)2 Fe
(b) (η5-C5H5)2, Co
(c) (η5-C5H5)2, Ru
(d) (η5-C5H5)2,Co+
Q4. Complex in which organic ligand is having only ϭ-bond with metal is:
(a) W (CH3)6
(b) (η5-C5H5)2 Fe
(c) K[PtCl3(C2H2)]
(d) (η6-C6H6)2 Ru
5. Among the metals Mn, Fe, Co and Ni, the ones those would react in its native form directly with
CO giving metal carbonyl compounds are:
(a) Co and Mn
85
(b) Mn and Fe
(c) Fe and Ni
(d) Ni and Co
6. In the H2Ru6(CO)18 cluster, containing 8-coordinated Ru centers, the hydrogen atoms are
(a) Both terminal
(b) One terminal and the other bridging
(c) Both bridging between two Ru centers
(d) Both bridging between three Ru centers.
7. In the hydroformylation reaction, the intermediate CH3CH2CH2 Co(Co)4:

(a) Forms are acyl intermediate CH3CH2CH2COCo (CO)3
(b) Forms an adduct with an olefin reactant.
(c) Reacts with H2
(d) Eliminates propane.
8. In Ziegler-Natta catalysis the commonly used catalyst system is:

(a) TiCl4, Al(C₂H5)3
(b) (η5-Cp)2TiCl2, Al(OEt)3
(c) VO(acac)2, Al2(CH3)6

(d) TiCl4, BF3
[CSIR DEC 2011]
9. The correct combination of metal, number of carbonyl ligands and the charge for a metal
z-
carbonyl complex [M(CO)x] that satisfies the 18 electron rule is
(a) M= Ti, x=6, z=1
(b) M= V,x=6, z=1
(c) M=Co, x=4, z=2
(d) M= Mo, x=5, z=1
86
10.The stable cyclopentadienyl complex of beryllium is

(a) [Be(η2-C5H5)2]
(b) [Be(η2-C5H5) (η3-C5H5)]
(c) [Be(η1-C5H5) (η3-C5H5)]
(d) [Be(η1-C5H5) (η5-C5H5)]
11. Reaction of Fe(CO)5 with OH leads to complex A which on oxidation with MnO2 gives
B.Compounds A and B respectively are
-
(a) [HFe(CO) 4] and Fe3(CO)12
-
(b) [Fe(CO) 5(OH)] and Fe2(CO)10
-2
(c) [Fe(CO)4] and Mn2(CO)10
-
(d) [HFe(CO)4] , and Fe2O3
12.The number of metal-metal bonds in the dimers, [CpFe(CO)(NO)]2 and [CpMo(CO)3]2

respectively, are
(a) two and two
(b) two and three
(c) one and two
(d) zero and one
13. In the trans-PtCl2L(CO) complex, the CO stretching frequency for L=NH3 , pyridine, NMe3
decreases in the order.
(a) pyridine> NH3 > NMe3
(b) NH3 > pyridine > NMe3
(c) NMe3 > NH3 > pyridine
(d) pyridine > NMe3 > NH3
87
14.The catalyst involved in carrying out the metathesis of 1-butene to give ethylene and 3-hexene
is:
(a)
(b) Na2PdCl4
(c) Co₂(CO) 2 ,H₂
(d) RhCl(PPh3)2
15. The greater stability of ((CH3) 3 C-CH2-)4 Ti(A) compared to that of ((CH3) 2CH-CH2 -)4 Ti(B)
is due to
(a) Hyperconjugation present in complex (A)
(b) β-hydride elimination is not possible in complex (A)
(c) Steric protection of titanium from reactive species in complex (A)
(d)The stronger nature of Ti-C bond in complex (A).
16. A compound A having the composition FeC9H8O3 shows one signal at 2.5 ppm and another one
around 5.0 ppm in its 1H NMR spectrum. The IR spectrum of this compound shows two bands
around 1680 cm-1. The compound follows the 18 electron rule of the following statements for A,
the correct one is/are
(A) It has η5-Cp group.
(B) It has a terminal CO ligand.
(C) It has a CH3 ligand
(D) It has Fe-H bond.
(a) (A) and (B) only
(b) (C) only
(c) (A) and (C) only
88
(d) (B) and (D) only
[CSIR JUNE 2012]

17. The reactions of Ni(CO) 4 with the ligand (L= PMe3 or P(OMe) 3 ) L yields Ni(CO) 3L. The
reaction is
(a) Associative
(b) Dissociative
(c) Interchange (Ia)
(d) Interchange (Id)
18. Among the following the strongest oxidizing agent is:

(a) [WO4] -2
(b) [CrO4] -2
(c) [MoO4] -2
(d)[ReO4] -2
19. For the reaction, trans-[IrCl(CO)(PPh3)2] + Cl 2 → trans - [IrCl 3(CO)(PPh 3) 2]the correct
observation
(a) ῡ co (product) > ῡ co (reactant)
(b) ῡ co (product)< ῡ co (reactant)
(c) ῡ co (product) = ῡ co (reactant)
(d) ῡ co (product) = ῡ co (free CO)
20. The carbonyl resonance in 13C NMR spectrum of [(η5-C5H5)]Rh(CO)]3 (103Rh, nuclear spin,
I=1/2, 100 %) shows a triplet at -65° C owing to the presence of
(a) Terminal CO
(b) µ₂-CO
(c) µ₂-CO
(d) η5-C5H5
89
21.The cluster having arachno type structure is:

(a) [Os5(CO) 16]
(b) [Os3(CO) 12]
(c) [Ir4(CO)12,]
(d) [Rh6(CO) 16]
22. The final product of the reaction [Mn(CO)6]+ +MeLi → is:

(a) [Mn (CO)6]+ Me-
(b) [Mn(CO)5Me]
(c) [Mn(CO)6]
(d) [(MeCO)Mn(CO)5]
23.The reaction 3[Rh4(CO)12]→2[Rh6(CO)16]+4CO [25°C, 500 atm CO] is:

(a) Exothermic as more metal-metal bonds are formed.
(b) Endothermic as stronger metal-carbonyl bonds are cleaved while weaker metal-metal bonds
are formed.
(c) Is entropically favorable but enthalpically unfavorable such that (ΔG=0)
(d) Thermodynamically unfavourable (ΔG>0).
24.The complex that DOES NOT obey 18- electron rule is:
(a) [(η5 –C5H5 )RuCl(CO)(PPh3)]
(b) [W(CO)3(SiMe3)(Cl)(NCMe)2]
(c) [IrCl3(PPh3)2(AsPh)2]-
(d) [Os(N)Br2(PMe3)(NMe2)]-
[CSIR DEC 2012]

25.The substitution of η5-Cp group with nitric oxide is the easiest for
(a) (η5-Cp2)Fe
90
(b) (η5-Cp2)CoCl
(c) (η5-Cp2)Ni
(d) (η5-Cp2)Co
26.The molecule
Follow 18 electron rule. The two 'M' satisfying the condition are
(a) Cr, Re+
(b) Mo, V
(c) V, Re+
(d) Cr, V
27.Complexes of general formula, fac-[Mo(CO)3(phosphite)3] have the C-O stretching bands given
below.
Phosphines: PF3(A) ; PCl3 (B); P(Cl)Ph2 (C); PMe3 (D)
ῡ (CO), cm-1: 2090(i) ; 2040(i); 1977(iii); 1945(iv)
The correct combination of the phosphine and the stretching frequency is,
(a) (A-i), (B-ii), (C-iii), (D-iv)
(b) (A-ii), (B-i), (C-iv), (D-iii)
(c) (A-iv), (B-iii), (C-ii), (D-i)
(d) (A-iii), (B-iv), (C-i), (D-ii)
28. In the cluster [Co3(CH)(CO)9] obeying 18e rule, the number of metal-metal bonds and the
bridging ligands respectively, are
(a) 3 and 1 CH
(b) 0 and 3 CO
(c) 3 and 1 CO
91
(d) 6 and 1 CH
29 For the following molecule :
Consider the following statements about its room temperature spectral data.
(A) 1H NMR has singlets at 5.48 and 3.18 ppm
(B) 1H NMR has multiplet at 5.48 and singlet at 3.18 ppm
(C) IR has CO stretching bands at 1950 and 1860 cm-1
(D) IR has only one CO stretching band at 1900 cm-1
The correct pair of statement is,
(a) A and C
(b) B and C
(c) A and D
(d) B and D
30. Consider the catalyst in column-I and reaction in column-II

Column-I Column-II
A [(R)-BINAP] Ru-2 i. Hydroformylation.
B [Rh(CO)2I2]-1 ii. asymmetric hydrogenation
C [Pd(PPh3)4] iii. Asymmetric hydrogen transfer
92
D iv heck coupling
The best match of a catalyst of column-I with the reaction nuclear column-II is
(a)(A-ii), (B-i), (C-iv), (D-iii)
(b) (A-i), (B-ii), (C-iii), (D-iv)
(c) (A-iii), (B-i), (C-iv), (D-ii)
(d) (A-iv), (B-iii), (C-ii), (D-i)
31.Consider the following reaction mechanism
The steps A, B and C, respectively, are

(a) Oxidative addition; transmetallation; reductive elimination.
(b) Oxidative addition; carbopalladation; β-hydride elimination.
(c) Carbopalladation; transmetallation; reductive elimination.
(d) Metal halogen exchange; transmetallation; metal extrusion.
32.Which one of the following will NOT undergo oxidative addition by methyl iodide?
(a) [Rh(CO)2I2]-
93
(b) [Ir(PPh3)2(CO)Cl]
(c) [(η2-CpRu(CO)2]
(d) [(η5 -Cp2Ti(Me)Cl]
33. In hydrofomylation reaction using [Rh(PPh3)2(CO)(H)] as the catalyst, addition of excess PPh3,
would
(a) increase the rate of reaction
(b) decrease the rate of reaction.
(c) not influence of the rate of reaction
(d) stop the reaction.
34. Reactions A and B are, termed as respectively.
(a) Insertion, Metathesis

(b) Metathesis, insertion
(c) Oxidative, addition, metathesis
(d) Oxidative addition, insertion
[CSIR JUNE 2013]
35 In the metal-olefin interaction, the extent of increase in metal olefin -back-donation would
(a) lead to a decrease in C=C bond length
(b) change the formal oxidation state of the metal
(c) change the hybridisation of the olefin carbon from sp² to sp³.
94
(d) increase with the presence of electron donating substituent on the olefin.
36. The oxidation state of molybdenum in [(η7- tropylium)Mo(CO) 3]+ is:

(a) +2
(b) +1
(c) 0
(d)-1
37. The reaction, [(CO)5 Mn (Me)] + CO→[(CO) 5 Mn {C(O)Me}]is an example for

(a) oxidative addition
(b) electrophilic substitution
(c) nucleophilic substitution
(d) migratory insertion
38. The orders of reactivity of ligands, NMe3 PMe3, and CO with complexes MeTiCl, and
(CO)5Mo (thf) are
(a) CO > PMe3 > NMe3 and CO > NMe3 > PMe3,
(b) PMe3 > CO > NMe3 and NMe3 > CO > PMe3
(c) NMe3 > PMe3 > CO and CO > PMe3 > NMe3
(d) NMe3 > CO> PMe3 and PMe3 > NMe3 > CO
39. The number of metal-metal bonds in [W2(OPh)6] is:

(a) 1
(b) 2
(c) 3
(d) 4
40. The number of metal-metal bonds in Ir4(CO)12 is

(a) 4
95
(b) 6
(c) 10
(d) 12
[CSIR DEC 2013]

41. The bond order of the metal-metal bond in the dimeric complex [ Re2Cl4(PMe2Ph) 4] is
(a) 4.0
(b) 3.5
(c) 3.0
(d) 2.5
42. Which of the following in NOT suitable as catalyst for hydroformylation?

(a) HCo(CO) 4
(b) HCo(CO)3PBu3
(c) HRh(CO)(PPh3)3
(d) H2Rh(PPh3)2Cl
43. In a cluster, H3CoRu3(CO) 12 total number of electrons considered to

be involved in its formation is
(a)57
(b) 60
(c) 63
(d) 72
44. Among the following clusters,

A=[(H)Co6 (CO) 15] B =[(H) 2Os6 (CO) 18] C=[(H) 2 Os5 (CO) 16]
H is encapsulated in
(a) A only
(b) B only
96
(c) B and C only

(d) A and B only
45. The correct statement regarding terminal/bridging CO groups in solid Co4(CO) 12 and Ir4(CO)
12 is
(a) both have equal number of bridging CO groups

(b) number of bridging CO groups in Co4(CO) 12 is 4
(c) the number of terminal CO groups in Co4(CO) 12 is 8
(d) the number of bridging CO groups in Ir4(CO) 12 is zero.
+
46. The electrophile Ph3C reacts with [(η5-C5H5 ) Fe(CO) 2 (CDMe2)] to give a product A. The
product A is formed because
(a) Fe is oxidized
(b) alkyl is susbtituted with Ph3C
(c) Fe-Ph bond is formed
(d) Alkyl is converted to alkene
47. Among the following, the correct statement is

(a) CH is isolobal to Co(CO3)
(b) CH2 is isolobal to Ni(CO) 2
(c) CH is isolobal to Fe(CO4)
(d) CH2 is isolobal to Mn(CO) 4
48. Subsitution of L with other ligands will be easiest for the species
(a)
97
(b)
(c)
(d)
49. Reaction of Ph2PCH2CH2PPh2 with [RhCl(CO)2]2 in a 2:1 molar ratio gives a crystalline solid
31 1
A. The IR spectrum of complex A shows νco at 1985 cm-1. The P( H) NMR spectrum of A consists
103
of two doublets of doublets of equal intensities ( Rh is 100% abundant and I =1/2 ). The
structure of complex A is
(a)
(b)
(c)
98
(d)
50. On reducing Fe3(CO) 12 with an excess of sodium, a carbonylate ion is formed. The iron is
isoelectronic with
-
(a) [Mn(CO)5]
(b) [Ni(CO) 4]
+
(c) [Mn(CO)5]
–
(d) [V(CO)6]
[CSIR JUNE 2014]
51. The ligand(s) that is (are) fluxional in [(η5-C5H5)(η-C5H5)Fe(CO)2] in the temperature range
221-298K, is (are)
(a) η5-C5H5
(b) η1-C5H5
(c) η5-C5H5 and CO
(d) η1C5H5 and CO
52. The typical electronic configurations of the transition metal centre for oxidative addition
(a) d0 and d8
(b) d6 and d8
(c) d8 and d10
(d) d5 and d10
53. The oxidation state of Ni and the number of metal-metal bonds in [Ni2(CO) 6] 2-
99
that are consistent with the 18 electron rule are

(a) Ni (-II), I bond
(b) Ni(IV), 2 bonds
(c) Ni(-I), 1 bond
(d) Ni(IV), 3 bonds
2 4 2 2
54. The compound [Re2(Me2PPh) 2CI4] (M) having a configuration of ϭ π δ δ* can be oxidized
to M+ and M2+. The formal metal-metal order in M ,M+ and M+2 respectively, are
(a) 3.0, 3.5 and 4.0 (b) 3.5, 4.0 and 3.0 (c) 4.0, 3.5 and 3.0 (d) 3.0, 4.0 and 3.5
[Re2(Me2PPh) 2CI4] = (M)
55. The total valence electron count and the structure type adopted by the complex [Fe3 (CO)15C)]
respectively, are
(a) 74 and nido
(b) 60 and closo
(c) 84 and arachno
(d) 62 and nido
56. 1H NMR spectrum of [η5-C5H5Rh)(C2H4)2] at -20°C shows a typical AA' XX' pattern in the
olefinic region. On increasing the temperature to -70°C, the separate lines collapse into a single
line which is due to
(a) free rotation of the ethylene ligand about the metal-olefin bond
(b) interamolecular exchange between the ethylene ligands
(c) intermolecular exchange between the ethylene ligands
(d) change in hapticity of the cyclopentadienyl ligand
57. Amongst the following which is not isolobal pairs

(a) Mn(CO)5 , CH3
(b) Fe(CO)4 , O
(c) Co(CO)3 , R2Si
100
(d) Mn(CO)5 , RS
[CSIR DEC 2014]

58. The hepticities ‘x’ and ‘y’ of the arene moieties in the diamagnetic complex
[(ηx-C6H6 )Ru(ηy-C6H6)] respectively are
(a) 6 and 6
(b) 4 and 4
(c) 4 and 6
(d) 6 and 2
∆
59.The rate of the reaction Ni(CO)4 + PPh3 [Ni(CO)3(PPh3)] + CO depends on
(a) Concentration of both the reactants
(b) Concentration of Ni(CO) 4 only
(c) Concentration of PPh3 only
(d) The steric bulk of PPh3
60 The product of the reaction of propene, CO and H2 in the presence of Co2(CO) 8 as a catalyst
is
(a) Butanoic acid
(b) Butanal
(c) 2-butanone
(d) Methylpropanoate
61. The point group symmetries for trans-[Cr(en) 2F2] + and [TiCl6] -3, respectively, are
(a) D4d and D3d
(b) D3d and D4d
101
(c) D4h and D3h

(d) D3h and D4h
62 Co4(CO)12 adopts the

(a)closo-structure
(b) nido-structure
(c) arachno-structure
(d) hypho-structure
63. Reductive elimination step in hydrogenation of alkenes by Wilkinson catalyst results in

(neglecting solvent in coordination sphere of Rh)
(a) T-shaped [Rh(PPh3) 2Cl]
(b) Trigonal-planar [Rh(PPh3) 2Cl] 2+
(c) T-shaped [Rh(H)(PPh3)Cl] +
(d) Trigonal-planar [Rh(H)(PPh3)2]
64. NaI(η5-C5H5)Fe(CO) 2] reacts with Br2 to give A. Reaction of A with LiAlH4 results in B. The
proton NMR spectrum of B consists of two singlets of relative intensity 5:1. Compounds A and B
respectively, are
(a) (η5-C5H5 ) Fe(CO)2Br, and (η5- C5H5 )Fe(CO)2H
(b) (η4-C5H5)Fe(CO) 2Br2 and (η4-C5H5)Fe(CO)2HBr
(c)( η5-C5H5)Fe(CO)2Br and (η4-C5H5)Fe(CO) 2(H)2
(d) (η5-C5H5 )Fe(CO)2Br and (η5-C5H5)Fe(CO)2HBr
65.The compound that undergoes oxidative addition reaction in presence of H2, is

(a) [Mn(CO)5]-1
(b) [(η5-C5H5 )MCO3]-1
(c) [IrCl(CO)(PPh3)2]
(d) [(η5-C5H5) 2ReH]
102
66.1H NMR spectrum of free benzene shows a peak at 7.2 ppm. The expected chemical shift (in
ppm) of C6H6 ligand in 1H NMR spectrum of [(η6-C6H6)Cr(CO)3] and the reason for it, if an, is/are
(a) 4.5; disruption of ring current
(b) 9.0; inductive effect
(c) 7.2
(d) 2.5 combination of inductive effect and disruption of ring current.
67.According to Wade's rule, anion C2B9H12 adopts

(a) closo-structure
(b) nido-structure
(c) arachno-sturcture
(d) hypho-structure
68.The final product in the reaction of [Cp ThH] with CO in an equimolar ratio is
(a)
(b)
(c)
(d)
69.Complexes HM(CO) 5 and [((η5-C5H5)M'(CO) 3] 2 obey the 18-electron rule. Identify M and M'
and their 1H NMR chemical shifts relative to TMS.
(a) M = Mn, -7.5; M'= Cr, 4.10
103
(b) M= Cr, -4.10; M'= Mn, -7.5

(c) M=V, -7.5; M'= Cr, 4.10
(d) M= Mn, -10.22 M'= Fe, 2.80
[CSIR JUNE 2015]

70. The binding modes of NO in 18 electron compounds [Co(CO)3(NO)] and [Ni(η5-Cp) (NO)],
respectively, are
(a)linear and bent
(b) bent and linear
(c) linear and linear
(d) bent and bent
71. The role of copper salt as co-catalyst in Wacker process is

(a) oxidation of Pd(0) by Cu(II)
(b)oxidation of Pd(0) by Cu(I)
(c) oxidation of Pd(II) by Cu(I)
(d) oxidation of Pd(II) by Cu(II)
72. For typical Fischer and Schrock carbenes, consider the following statements
A. Oxidation state of metal is low in Fischer carbene and high in Schrock carbene
B. Auxilliary ligands are π-acceptor in Fischer carbene and non π acceptor in Schrock carbene
C. Substituents on carbene carbon are non π donor in Fischer carbene and π donor in Schrock
carbene
D. Carbene carbon is electrophilic in Fischer carbene and nucleophilic in Schrock carbene
(a) A, B and C
(b) A, B and D
(c) B. C and D
(d) A, C and D
104
73. The refluxing of RhCl3.3H2O with an excess of PPh3, in ethanol gives a complex A. Complex A
and the valence electron count on rhodium are, respectively.
(a) [RhCl(PPh3) 3], 16
(b) [RhCl(PPh3) 5], 16
(c) [RhCl(PPh3) 3], 18
(d) [RhCK(PPh3) 5], 18
74. The β-hydrogen elimination will be facile in
(a)
(b)
(c)
(d)
75. The reaction [Co(CN) 5H2O] 2- +X- → [Co(CN)5X] 2- +H2O follows a/an
(a) Interchange dissociative (Id) mechanism
(b) Dissociative (D) mechanism
(c) Associative (A) mechanism
(d) Interchange Associative (Ia) mechanism
76. According to Wade's theory the anion [B12H12] 2- adopts

(a) closo-structure
105
(b) arachno-structure
(c) hypo-structure
(d) nido-structure
77. The reaction of SbCl3, with 3 equivalents of EtMgBr yields compound X. Two equivalents of
SbI3 react with one equivalent of X to give Y. In the solid state, Y has a 1D-polymeric structure in
which each Sb is in a square pyramidal environment. Compounds X and Y respectively, are
(a) SbEt3, and [Sb(Et)I2]n
(c) SbEt3, and [SbEt2Br2] n
(b) Sb(Et2)Cl and [Sb(Et)Cl] n
(d) Sb(Et)Br2 and [SbEt(I)(Br)] n
78. The following statements are given regarding the agostic interaction C-H----Ir observed in
[Ir(Ph3P)3Cl].
(A) Upfield shift of C-H proton in 1H NMR spectrum
(B) Increased acid character of C-H
(C) ῡ co- in IR spectrum shifts to higher wavenumber
The correct answer is/are:
(a) A and C
(b) B and C
(c) A and B
(d) C only
79. Match column A (coupling reactions) with column B (reagents)

Column-A Column-B
(1) Suzuki coupling (I) H₂C=CHCO CH

(2) Heck coupling (II) RB(OH),
(3) Sonagashira coupling (III) PhCO(CH) Znl
106
(4) Negeshi coupling (IV) CHECR

(V) SnR
The correct match is:
(a) I-II, 2-1, 3-IV, 4-III
(b) 1-1, 2-V. 3-III, 4-IV
(c) 1-IV, 2-III, 3-11, 4-1
(d) 1-11.2-111, 3-IV,4-V
80. Amongst the following

(A) [Mn(η5-Cp)(CO)3]
(B) [Os (η5-Cp) 2]
(C) [Ru (η5-Cp) 2] and
(D) [Fe(η5-Cp) 2]
the compounds with most shielded and deshielded Cp protons respectively, are
(a) D and A
(b) D and B
(c) C and A
(d) C and B
81. Total number of vertices in metal clusters [Ru6(C)(CO)17] [Os5(C)(CO)15] and

[Ru5(C)(CO) 16] are 6, 5 and 5, respectively. The predicted structures of these complexes,
respectively are
(a) closo, nido and nido
(b) closo, nido and arachno
(c) arachno, closo and nido
(d) arachno, nido and closo
82. The reductive elimination of Ar-R (coupled product) from A is facile when
107
(a) R = CH3
(b) R = CH2Ph
(c) R CH2COPh
(d) R = CH2CF3
83. The least probable product from A on reductive elimination is
84. With respect to and bonding in Pt III in the structure given below, which of the following
represent the correct bonding diagram
(a) M(ϭ)→ L(ϭ) and M(π)→ L(π*)

(b) L(ϭ)→M(π) and L(π)→M(π)
(c) L(π) → M(π) and L(ϭ)→ M(π)
108
(d) L(π)→ M(ϭ) and M(π)→ L(π*)
[CSIR DEC 2015]

85. The W-W bond order in [W(η5-C5H5)(µ-Cl)(CO) 2]2 is
(a) three
(b) two
(c) one
(d) zero
86. For the reaction of [Fe(η5-C5H5)(CH3)(CO)2] with PMe3, the main intermediate is
(a) [Fe(η5-C5H5)(CH3)(CO)2 (PMe3)]
(b) [Fe(η5-C5H5)(COCH3)(CO)]
(c) [Fe(η3-C5H5)(CH3)(CO) 2]
(d) ) [Fe(η3-C5H5)(COCH3)(CO)(PMe3)]
87. [(η3-C3H5)Mn(CO)4] shows fluxional behavior. The 'H NMR spectrum of this compound when
it is in the non-fluxional state shows-
(a) one signal
(b) two signals in the intensity ratio of 4: 1
(c) three signals in the intensity ratio of 2: 2 : 1
(d) five signals of equal intensity.
88. Using Wade's rules predict the structure type of [C2B5H7 ]

(a) nido
(b) closos
(c) arachno
(d) hypho
89. For uranocene, the correct statement(s) is/are

109
(A) oxidation state of uranium is ‘+4’

(B) it has cyclooctatetraenide ligands
(C) it is bent sandwich compound
(D) it has ‘-2’ charge.
Correct answer is
(a)A and B
(b) B and C
(c) A and D
(d) B only
- -
90. The final products of the reaction of carbonyl metalates [V(CO) 6] and [Co(CO) 4] with
H3PO4 respectively, are
(a) V(CO) 6 and HCo(CO)4
(b) HV(CO)6 and Co2 (CO)8
+
(c) [H2V(CO)6] and HCo(CO)4
(d) V(CO)6and Co2(CO)8
91. The number of valence electrons provided by [Ru(CO)3] fragment towards cluster bonding is
(a) 1
(b) 14
(c) 6
(d) 2
92. The intermediate and the final major product of photolysis of Z
From the following are

110
(a) A and D
(b) B and D
(c) B and C
(d) A and C
93. Reaction of [Mn2(CO)10], with I2, results in A without loss of CO. Compound A, on heating of
120°C loses a CO ligand to give B, which does not have a Mn-Mn bond. Compound B reacts with
pyridine to give 2 equivalents of C. Compounds A, B and C from the following respec tively, are
(a) II, V and IV

(b) II, III AND IV
(c) V, III and IV
(d) II. V and III
-1
94. The approximate positions of νco bands (cm ) in the solid-state infrared spectrum and the Fe-
Fe bond order in [Fe(η5-C5H5)(µ-CO)(CO)]2 (non-centrosymmetric) respectively,are
(a) (2020, 1980, 1800) and one
(b) (2020, 1980, 1800) and two
(c) (2020, 1980) and one
(d) (2143) and one
111
[CSIR-JUNE 2016]
95. Identify the species, those obey the 18 electron rule, from the following:
(a) A and B
(b) B and C
(c) C and D
(d) A and D
96. The following transformation
is an example of
(a) oxidative addition
(b) insertion
(c) β-hydride elimination.
(d) reductive elimination.
97. CpM [Cp is (η5-C5H5)] fragment isolobal with a BH fragment is

(a) CpGe
(b) CpMn
(c) CpRu
(d) CpCo
98. The number of metal-metal bonds in [Co2Fe2(CO)11(η4-PPh)2] is

112
(a) 3
(b) 4
(c) 5
(d) 6
99. Choose the correct option for carbonyl fluoride with respect to bond angle and bond length
(a) ∠F-C-F > ∠F-C-O and C-F > C-O
(b) ∠F-C-F > ∠F-C-O and C-F < C-O
(c) ∠F-C-F < ∠F-C-O and C-F > C-O
(d) ∠F-C-F < ∠F-C-O and C-F < C-O
100. Correct order of M-C bond length of metallocenes (a-c)

1. [Fe(η5-Cp)2]
2. [Ni(η5-Cp)2]
3. [Co(η5-Cp)2] is—
(a) A> B >C
(b) B > C >A
(c) C> B >A
(d) A> C > B
101. The 1H NMR spectrum of [Ru(η4-C8H8)(CO)3] at 23°C consists of a sharp single line. The
number of signals observed at low temperature (-140 °C) in its spectrum is
(a) 8
(b) 6
(c) 4
(d) 2
102. The numbers of skeletal electrons present in the compounds C2B3H5 , C2B4H6 , and B5H9 are,
respectively
(a) 10, 12 and 12
(b) 12, 14 and 14
113
(c) 10, 12 and 14

(d) 12, 14 and 12
103. For fluxional Fe(CO)5 (structure given below) in solution, the exchange of numbered CO
groups will be between
(a) 2 and 5; 3 and 4.

(b) 2 and 3; 4 and 5
(c) 2 and 3; 1 and 5
(d) 1 and 2; 4 and 5
104. In the following reaction sequence

𝑲𝑶𝑯 𝒂𝒒 𝒔𝒐𝒍𝒏
HNEt2 + CS2 P R
[𝑪𝒑𝑴𝒐(𝑪𝑶)𝟑]𝟐
I2 S
where dtc= dithiocarbamate and tds = thiuramdisulfide.

Identify P, R and S. Cp= η5- C5H5
114
105. Reaction of Cr(CO)6 with LiC6H5 gives A which reacts with [MeO][BF] to give B. The
structures of A and B respectively, are
106. Heating a sample of [(η5- C5H5)Mo(CO)3]2 results in the formation of [(η5- C5H5)Mo(CO)2]
with elimination of 2 equivalents of CO. The Mo- Mo bond order in this reaction changes from
(a) 2 to 3.
(b) 1 to 2
(c) 1 to 3
115
(d) 2 to 4
107. A plausible intermediate involved in the self metathesis reaction of C5H5-C≡C-C6H4-p Me

catalyzed by [(tBuO)3W≡C-tBu] is –
[CSIR DEC 2016]

108. The number of bridging ligand(s) and metal-metal bond(s) present in the complex Ru2 (η5-
Cp)2(CO)2(Ph2PCH2PPh2 )] (obeys 18-electron rule), respectively, are
(a) 0 and 1
(b) 2 and 1
(c) 3 and 1
(d) 1 and 2
109. The rate of alkene coordination to [PtCl4]-2 is highest for

116
(a) norbornene
(b) ethylene
(c) cyclohexene
(d) 1-butene
110. Consider the following statements, I and II:

I: [Rh(CO)2 I2]- catalytically converts CH3I and CO to CH3COI
II: [Rh(CO)2I2]- is diamagnetic in nature
The correct from the following is
(a) I and II are correct and II is an explanation of I
(b) I and II are correct and II is not an explanation of I
(c) I is correct and II is incorrect
(d) I and II are incorrect
111. The geometry of [ReH9]-2 is

(a) monocapped square antiprism
(b) monocapped cube
(c) tricapped trigonal prism
(d) heptagonal bipyramid
112. According to isolobal analogy, the right set of fragments that might replace Co(CO)3 in
[Co4(CO)12] is
(a) CH, BH and Mn(CO)5
(c) Fe(CO)4, CH2 , and SiCH3
(b) P, CH and Ni(η5- C5H5)
(d) BH, SiCH3 and P
113. According to Wade's rules, the correct structural types of [Co(η5- C5H5)B4H8] and
117
[Mn(η2-B3H8)(CO)4] are
(a) closo and nido
(b) nido and arachno
(c) closo and arachno
(d) nido and nido
114. The correct geometry of [Rh6C(CO)15]-2 is

(a) octahedron
(b) pentagonal pyramid
(c) trigonal prism
(d) monocapped square pyramid
115. Product A in the following reaction is
(a) D2C=CD2
(b) D3C-CD3
(d) H₂C=CD₂
116. Treatment of Fe(CO)5 with 1, 3-butadiene gives B that shows two signals in its 1H NMR
spectrum. B on treatment with HCl yields C which shows four signals in its 1H NMR spectrum.
The compound C is
118
[CSIR JUNE 2017]

117. Choose the isoelectronic pair among the following:
A. [V(CO)6]
B. [Cu(η5- C5H5) (CO)]
C. [Co(CO)4]-
D. [IrCl (CO)(PPh3)]
(a) A and B
(b) B and C
(c) C and D
(d) A and D
118. An organometallic fragment that is isolobal to CH3+ is

(a) [Fe(CO)5]
(b) [Mn(CO)5]
(c) [Cr(CO)5]
(d) [Ni(CO)3]+
119. Reaction of Na[Mn(CO)5] with H3C=CHCH2Cl gives A along with NaCl. Photolysis of com
pound A results in compound B together with elimination of CO. The correct structural
formulations of compounds A and B are respectively,
119
120. The number of bonding molecular orbitals and the number of available skeletal electrons in
[B6H6]-2, respectively, are:
(a) 7 and 14
(b) 6 and 12
(c) 18 and 12
(d) 11 and 14
121. Addition of NaBH4 to [(η5-Cp)Fe(η6-C6H6)]+ will give

(a) [(η5-Cp)Fe(H)2]
(b) [(η5-Cp) Fe(H)( η6-C6H6)]
(c) [(η5-Cp) Fe(η6-C6H6)]
(d) [(η5-Cp) Fe(η6-C6H7)]
122. The µeff [Fe(S2CNEt2)3] changes with temperature with the involvement of two electronic
states. The states are
(a) low spin 2T2g and high-spin 6A1g
(c) low spin 2Eg and high-spin 6A1g
(b) low spin 1A1g and high-spin 3T2g
(d) low spin 2T2g and high-spin 4T1g
123. Identify the product in the reaction between

120
[CSIR DEC 2017]

124. In trigonal prismatic ligand field, the most stabilized d orbital is
(a) dz2
(b) dxy
(c) dxz
(d) dyz
125. Among the following species isolobal to CH2 are

A. CpCr(CO)2
B. CpCu
C. Ni(CO)2
D. Cr(CO)4
E. Fe(CO)4
(a) A, C and E
(b) B, C and D
(c) B, C and E
(d) A, B and D
126. In the complex [Pd(L-L)(Me)(Ph)], the bisphosphine (L-L) that does not allow reductive
elimination of PhMe is
121
(a)
(b)
(c)
(d)
127. According to Wade's rules, the cluster type and geometry of [Sn9]-4 , respectively, are
(a) closo and tricapped trigonal prismatic
(b) nido and monocapped square-antiprismatic
(c) arachno and heptagonal bipyramidal
(d) closo and monocapped square antiprismatic
[CSIR JUNE 2018]

128. The correct of C-O bond length is-
122
1. H3B.CO > [Mn(CO)6]+ > [Cr(CO)6] > [V(CO)6]-

2. [V(CO)6]- > [Cr(CO)6] > [Mn(CO)6]+ >H3B.CO
3. [Mn(CO)6]+ > H3B.CO > [V(CO)6]- < [Cr(CO)6]
4. [Cr(CO)6] > [V(CO)6]- > H3B.CO > [Mn(CO)6]+
129. For the following reaction
The structure of the intermediate is
130. The correct increasing order of C-C bond length in the following molecules (A-D)
[PtCl3(C2H4)]- (A) , [Pt(PPh3)2 (C2H4)] (B) , [Pt(PPh3)2{C2(CH4)}] (C)
1. (C) < (A) <(B)
2. (A) < (B) < (C)
3. (B) < (C) < (A)
4. (C) < (B) < (A)
131. Which of the following are NOT closo clusters?

[{Co(η5-C5H5)}2(C2B6H8)] (A) [B4C2H8] (B) [B10H13 {(Au(PPh3)}] (C) [C2B8H10] (D)
123
1. (C) and (D)

2. (A) and (B)
3. (A) and (C)
4. (B) and (C)
132. Identify the pair of molecules which are isoelecronic as well as isostructural from the
following
[Pd(PPh3)4] (A) , [V(CO)6] (B), [Cr(CO)6] (C) , [Rh(PPh3)3Cl] (D) , [(η5-C5H5)Ni(NO)] (E),
Ni(CO)4 (F)
1. B and C
2. A and F
3. A and D
4. C and E
133. For the following reaction, correct statement (S) is/are
(A) Oxidation state of iridium increases from I to II

(B) It is 𝜷-hydride elimination reaction
(C) (I) and (II) both are diamagnetic
(D) It is migratory insertion reaction
1. (A) only
2. (A) and (C)
3. (C) and (D)
4. (B), (C), and (D)
124
134. The reaction of [(η5 – C5H5 (Fe(CO)2]- with CH3I gives compound A. The 1H NMR spectrum
of A show two singlets in an integrated intensity ratio of 3:5. Compound A upon reaction with
PPh3 give compound B. The 1H NMR spectrum of B shows 3 sets of signals in an integrated
intensity ratio of 3:5:15. Compounds A and B respectively, are
(a)
(b)
(c)
(d)
135. The structures of [Re2Cl8]-2 (A) and [Os2Cl8]-2 (B) are made up of two MCl4 units. For these
structure which statement is correct?
(a) (A) and (B) both have MCl4 units eclipsed.
(b) (A) and (B) both have MCl4 units staggered.
(c) (A) has both MCl4 units staggered and (B) has both MCl4 units eclipsed.
(d) (A) has both MCl4 units eclipsed and (B) has both MCl4 units staggered.
125
136. For the Wacker process, pick the correct statement (s) from the following:
(A) Pd(II) is reduced to Pd(0) by Cu(I)
(B) Pd(O) is oxidized to Pd(II) by Cu(II)
(C) Cu(II) promotes the reductive elimination
correct answer is
(a) A and C
(b) B and C
(c) A and B
(d) B Only
[CSIR DEC 2018]

137. The correct order of acceptor ability of the phosphorus ligands is
(a) PMe3 > PPh3 > P(OPh)3 > PF3
(b) PF3 > P(OPh)3 > PPh3 > PMe3
(c) PF3 > PMe3 > PPh3 >P(OPh)3
(d) P(OPh)3 > PF3 > PMe3 > PPh3
138. Identify the correct statement(s) for H3B.CO

(A) sp2 hybridized orbital of B accepts the lone pair of CO.
(B) Its ῡCO value is more than that for free CO
(C) Formal oxidation state of C is +4 in the compound
Answer is
(a) A and B
(b) B only
(c) A only
(d) A and C
139. The product for the reaction given below is

126
(a)
(b)
(c)
(d)
140. Match the following complexes with their vCO stretching frequency
The correct match is

(a) A-I, B-IV, C-II, D-III
(c) A-IV, B-III, C-I, D-II
(b) A-III, B-II, C-I, D-IV
(d) A-I, B-II, C-III, D-IV
141. The VCN in [Fe(CN)6]-3 (A) and [Fe(CN)6]-4 (B) and Vco in [Cr(CO)3(NH3)3] (C) and [Cr(CO)6]
(D) are compared below. The pair with correct order is
(a)A>B ;C>D
127
(b)A>B ;C<D
(c) A<B ;C>D
(d) A<B ; C<D
142. The cluster type and geometry of the species [Rh9P(CO)21]-2 are
(a) closo, tricapped trigonal prism
(b) arachno, trigonal prism
(c) nido, capped square antiprism
(d) nido, bicapped trigonal prism
143. Hydroformylation of 1-propene with [HRh(CO)L2]leads to linear and branched formylated

products. The linear hydroformylated product is formed with highest selectivity when 'L' in the
rhodium complex is
144. The hydrocarbon having an analogous structure to that of P4O6 is

(a) [(CH)4 (µ-CH₂)6]
(c) [(CH2)4 (µ -CH)6]
(b) [(CH)6 (µ -CH2)4]
(d) [(CH2)4 (µ -CH)4]
[CSIR JUNE 2019]

145. The number of Ni-Ni bonds in [CpNi(µ-PPh2)]2 complex obeying the 18 electron rule is
(a) 0
(b) 1
(c) 2
(d) 3
128
146. For the reaction of trans-[IrX(CO)(PPh3)2] (X= F, Cl , Br , I) with O2, correct order of
variation of rate with X is
(a) Br>I>F>Cl
(b) F>Cl>Br>I
(c)F≈Cl≈Br≈1
(d) I>Br>Cl> F
147. The organic species isolobal to [Fe(CO)2(PPh3)]- is

(a) CH2+
(b) CH-
(c) CH3
(d) CH
148. The correct statements about [Ru6C(CO)17] cluster from the following
(1) it is an 86 electron cluster
(2) it is a closo structure type
(3) its shape is capped square pyramid
(4) carbon interacts with all the Ru centres in the cluster
are
(a) 1, 2, 3 and 4
(b) 1 and 2 only
(c) 1, 2 and 3
(d) 1, 2 and 4
149. A plausible structure of the intermediate involved in the following reaction

[Fe(η5-C5H5)(CH3)(CO)2] + PPh3 → [Fe(η5-C5H5)(C(=O)CH3)(CO)( PPh3)]
129
150. Consider the following reactions:
The reaction(s) which will NOT produce ethane as a product is/are

(a) A
(b) B
(c) C
(d) A and C
151. Considering ϭ-bonding only, in the MO diagram of a metal complex with trigonal
bipyramidal (TBP) geometry, the d-orbitals which remain non-bonding are
(a) dz² and dxz
(b) dxz and dyz
(c) d x2-y2 and dxy
(d) dz² and dyz
[CSIR DEC 2019]

152. The expected number of co bands in the IR spectra of fac-[Mo(PPh3)2(CO)3] and trans-
[Mo(PPh3)2(CO)4] are, respectively
(1)one and one
(2)Two and two
(3)two and one
(4)three and one
130
153. The most stable vanadium species in aqueous medium is

(1) [V(H2O)5(OH)]+2
(2)[VO(H2O)5]+2
(3)[VO(H2O)5]+
(4)[V(H2O)4(OH)2]+2
154. The correct order of metal-carbon distance is

(1)Fe(η5-Cp)2 >Co(η5-Cp)2 >Ni(η5- Cp)2
(2)Fe(η5-Cp)2 > Ni(η5- Cp)2 >Co(η5-Cp)2
(3) Ni(η5- Cp)2 >Fe(η5-Cp)2 >Co(η5-Cp)2
(4)Ni(η5-Cp)2 >Co(η5-Cp)2 > Fe(η5-Cp)2
155.The rate-determining step in the catalytic synthesis of acetic acid by Monsanto process is
(1) oxidative addition of CH3I to [RhI2(CO)2]-
(2) migration of CH3 group to CO of [RhI3(CO)2(CH3)]-
(3) loss of CH3COI from [RhI3(CO)2(COCH3)]-
(4) coordination of CO to [RhI3CO(COCH3)]-
156. The cluster types of [Fe5(CO)14N]- and [Co6(CO)13N]- are, respectively,

(1)nido-, nido
(2)nido-, closo
(3)closo-, nido
(4)closo-, closo
157. The main product of nucleoplallic attack of H- on the complex ion given below is
131
(a)
(b)
(c)
(d)
[CSIR 2020]
158. The order of rate of substitution of chloride by pyridine (in ethanol) in the following
complexes is
(a) I>II>III
132
(b) I≈III≈II
(c) I>II≈III
(d) I<II≈III
159. Among the following complexes, the one showing the highest rate of substitution of a CO
ligand on heating with one equivalent of PPh3 in decalin, is
(a) (η5-C5H5)Mn(CO)3
(b) (η5-C5Ph5)Mn(CO)3
(c) (η5-C5Me5)Mn(CO)3
(d) (η5-indenyl)Mn(CO)3
160.The correct electronic configuration of frontier MO's of Mn(η5-C5Me5) is

(a) e2g2 a1g1e1g2
(b) e2g4 a1g1
(c) e2g3 a1g2
(d) a1g2e2g3
161. On heating [Mo(N2)2(PMe2Ph)4] and [ReCl(N2)(PMe2Ph)4], the products formed are

respectively
(a) [(η6-PhPMe2)Mo(PMe2Ph)3] and [(η6-PhPMe2)Re(PMe2Ph)3]Cl
(b) [(PMe2Ph)4Mo(µ-N2)2Mo(PMe2Ph)4] and [(PMe2Ph)4Re(µ-Cl)2Re(PMe2Ph)4]
(c) [(η6-PhPMe2)Mo(PMe2Ph)3] and [(PMe2Ph)4Re(u-Cl)2Re(PMe2Ph)4]
(d) [(PMe2Ph)4Mo(u-N2)2Mo(PMe2Ph)4] and [(η6-PhPMe2)Re(PMe2Ph)3]Cl
162.The geometry/shape of the Fe4 core of the cluster [Fe4C(CO)12]-2 is

(a) tetrahedron
(b) square pyramid
(c) butterfly
(d) trigonal bipyramid
163.The product A of the following reaction is

133
Is
(a)
(b)
(c)
(d)
164.The number of peaks with relative intensities observed in the 1H NMR spectra of
[(Cp)2Fe(CO)2] at + 30 °C and -80 °C in diethyl ether are, respectively
(a) two peaks (1:1) and four peaks (5:2:2:1)
(b) one peak and two peaks (1:1)
(c) two peaks (1:1) at both the temperatures
(d) one peak and four peaks (5:2:2:1)
165.The infrared (IR) spectrum of the product A for the following reaction
134
shows three STRONG bands at 1986, 1935 and 1601 cm-1 . The correct structure of 'A' is
(a)
(b)
(c)
(d)
135
[CSIR JUNE 2021]
166. Consider following statement(s) in the context of NO and CO ligands

A. In the bent mode, NO donates three electrons to the metal center.
B. In IR spectrum, the 𝒗𝑵𝑶for the bent nitrosyl ligand typically lies between 1525 and 𝟏𝟔𝟗0 𝒄𝒎−𝟏
C. The HOMO of NO and CO are 𝝅∗ and 𝝈 orbitals, respectively
(a) A only
(b) B and C
(c) A and C
(d) A and B
167. Consider the following statement (s) in the context of organometallic complex (x):
A. The carbene ligand donates two electrons to the metal and accepts d electrons to make a Pi-
bond
B. The C (carbene) is nucleophilic
C. Rotation around the Cr=c(OME)Me double bond has low barrier (< 10 kcal/mol) Correct
statement(s) is/are:
(a) A and B
(b) A only
(c) A and C
(d) B and C
168. The correct geometries for the metal carbonyl clusters, A-C
A. 𝑹𝒖𝟔 (𝑪𝑶)𝟏𝟕 𝑩 F
B. 𝑶𝒔𝟔 (𝑪𝑶)𝟏𝟖 𝑷 F
C. [𝑶𝒔𝟒 (𝑪𝑶)𝟏𝟔 ] are
(a) A: pentagonal bipyramidal, B: trigonal prismatic, and C:tetrahedral
(b) A: pentagonal bipyramidal, B: octahedral, and C: square
(c) A: octahedral, B: trigonal prismatic, and C: tetrahedral
(d) A: octahedral, B: trigonal prismatic, and C: square
169. Identify the thermodynamically stable structure of [ 𝜼𝟓 − 𝑪𝟓 𝑯𝟓 𝑭𝒆 𝝁𝟐 − 𝑪𝑶 (𝑵𝑶)]𝟐

136
(a) (b)
(c) (d)
170. The major product formed in the following reaction
(a)
(b)
(c)
(d)
171. The structure of the reactive intermediate generated by the reaction of CHCl3 and KOH is
(a)
(b)
137
(c)
(d)
CORRECT ANSWERS & EXPLANATIONS
1. Correct answer: (d)

Oxidation of metal is easier for electron rich systems, so electron rich metals undergo oxidative addition
and as reduction is easier for electron-deficient metal, so it undergoes reductive elimination.
2. Correct answer (c)

This is correct stability order because Ti(CH2Ph)4 has no 𝛽 −hydrogen .Hence no 𝛽 −elimination and
compound is stable whereas in Ti(i-Pr)4 has max no of 𝛽 −hydrogens followed by TiEt4 and TiMe4. So
Ti(i-Pr)4 undergoes fast 𝛽 −elimination hence least stable.
Ti(i-Pr)4 < TiEt4< TiMe4 <Ti(CH2Ph)4
3. Correct answer: (b)
Compound Number of electron in outer shell of

central atom
(η5-C5H5)2 Fe 18
(η5-C5H5)2Co 19
(η5-C5H5)2Ru 18
(η5-C5H5)2Co+ 18
Oxidation (loss of electrons) of (η5-C5H5)2, Co to (η5-C5H5)2 Co+ gives an 18

138
electron compound, (more stable) therefore easy to oxidise.

4. Correct answer: (a)
W(CH3)6 having 6 ϭ-bond with metal .
5. Correct answer: (c)

Ni+ 4CO →Ni(CO)4
Fe+5CO→ Fe(CO)5
Both Ni and Fe reacts directly with CO to give carbonyl compounds.
Electron cluster H2Ru6(CO)18 displays a distorted octahedral metal geometry.

Here each hydride ligand is connected to 3-Ru atoms.

During hydroformylation the intermediate CH3-CH2-CH2-Co(CO)4 gets transformed to acyl intermediate
CH3CH2CH2 -COCo(CO)3
139

Ziegler-Natta catalyst is TiCl4 , Al(C₂H5)3
9. Correct answer is (b).

M=V, x=6, z=1
i.e. [V(CO)6]-1 = 5+2x6+1=18
10. Correct answer is (d).
Because main group element follows octet rule.
[Be(η1-C5H5) (η5-C5H5)]
2+5+1=8
11. Correct answer is (a)

[CpFe(CO)(NO)]2
Step-1: Determine the total valence electron (TVE) = A
A=[5+8+2+3]x2=[18]x2=36
Step-2: B=(18n –A) where n number of metal.
B (2x18)-36 =36-36=0
No metal-metal bond found.
[CpMo(CO)3]2
Step-1: A [5+6+2x3] x2=[17]×2=34
Step-2: B= (18n-A)=2x18-34 = 36-34 = 2
Step-3: B/2 gives the total number of M-M bonds in the complex B =2/2=1
In this complex, the total number of M-M bonds is one
13. Correct answer is (a).

Order of donor ability NMe3 > NH3> pyridine
Order of CO stretching frequency pyridine > NH3 > NMe3
140

Option A is Ruthenium(II) carbenoid complexes, also known as Grubb’s Catalysts, they are widely used
for olefin methathesis.

Compound A does not have any β hydrogen, hence β-hydride elimination is not possible in compound
A, whereas compound B will undergo β-hydride elimination as follows

1
H-NMR giving one signal at 5.0ppm indicates presence of η5-Cp ring, another one signal at 2.5ppm
indicates presence of CH3 group. IR band at 1680cm-1 indicates presence of ketone (C=O) group. Thus
the appropriate structure of molecule.

Ni(CO) 4 Total valence electron around Ni 10+ 4x2=18 electron
Substitution reactions at coordinatively saturated tetrahedral complexes with a 18 electron count like
Ni(CO) 4, or Ni(CO)2(PR3)2 follows a simple first order kinetics.
141
Since rate does not depend upon the concentration and nature of the ligand suggesting a dissociative
mechanism.
18. Correct answer is (b)

In [WO4] -2 , [MoO4] -2, [ReO4] -2 [CrO4] -2all the metals have same oxidation state but Cr+6 is of
smallest size. Therefore it has strongest tendency to attract electrons. Therefore strongest oxidizing
agent.

Since in product metal Ir is present in the higher oxidation state. So, there is less back bonding to orbital
of CO.
Hence, ῡ (CO) product > ῡ (CO) reactant
20. Correct option (b)

Triplet of carbonyl carbon indicates the each CO is attached with chemically equivalent two Rh atoms
that means µ₂-CO complex. Actual structure is
142
21. Corret answer is (b)

[Os3(CO) 12]
Step-1: Calculate T.V.E. (total valency electron)
8x3 + 2×12 = 48
Step-II: Polyhedral electron count
T.V.E - (nx12) = 48-36=12 n=number of the metal atom
Step-III: =P.E.C./2=12/2 =6 = (n+3) =Archano.

Because metal carbonyls are stronger bond , to break this bond huge amount of energy are required. But
metal-metal bonds are weaker bond. So, reaction is endothermic and enthalpy predominant and entropy
unfavourable.

[(η5 –C5H5 )RuCl(CO)(PPh3)]
T.V.E = 5+8+1+2+2=18e-
[W(CO)3(SiMe3)(Cl)(NCMe)2]
143
T.V.E= 6+ 6+1+1+ 2x2 =18e-

[IrCl3(PPh3)2(AsPh2)]-
T.V.E= 9+ 3 +4+1+ 1 =18e-
[Os(N)Br2(PMe3)(NMe2)]-
T.V.E= 8+ 5 +2+1+ 1 =17e
25. Correct answer is (c)
26. Correct option (a)
ELECTRON COUNT = 2x5 +M+2 =18

M = 18-12 =6
So, M = Cr, Re+

As the π-accepting abilities of phosphine increases vC- O stretching frequency of the complex increases.
So, the order of n-accepting abilities among the given phosphine is:
PF3 > PCl3 > PClPh2 > PMe3
i.e. A>B>C>D.
So, the correct combination for vC- O stretching is:
A→2090
144
B→ 2040
C→ 1977
D→ 1945

The structure of cluster [Co3(CH)(CO)9]
So, the number of M-M bond = 3 and bridging ligand=1 CH
Since, the molecule is C2 -symmetric. So, two CO's will give two absorption band in IR spectrum.

[Rh(CO)2I2]-1 → Hydroformylation.
[Pd(PPh3)4] →Heck coupling (It is a catalyst for Heck coupling)
145

Step (A) is O.A. because the oxidation state of the metal is increased by two units.
Step(B) is transmetallation because the ligand is transferring from one metal to another metal. Step(C) is
reductive elimination because the oxidation state of the metal is increased by two units
32. Correct answer is (d)

(a)[Rh(CO)2I2]- →16e- and a better coordinate for O.A.
(b) [Ir(PPh3)2(CO)Cl] →16e- species (Vaska's complex) O.A. is possible.
(c) [(η2-CpRu(CO)2] →16e- system O.A. is not possible because metal in high oxidation state.
(d) [(η5 -Cp2Ti(Me)Cl] →18e- species as such O.A. is not possible but after the dissociation of ligand
‘CO’, O.A. is possible.
146
18 electron species in excess PPh3 it becomes 20 electron species but the active catalyst is 16 electron
species. So, in presence of excess PPh3 the rate of hydroformylation will be decreases.

Since SnCl2 will behaves as a carbene and it insert into the M-M bond. So, it is a kind of insertion
reaction.
35. Correct answer is (c).

In Metal-Olefin interaction, the extent of increase in metal → Olefin л-back donation would strengthen
the Metal-Olefin bond which produces a increase in C = C bond length and somewhat single bond
character which results a change in hybridisation from sp² to sp³.

[(η7- tropylium)Mo(CO) 3]
In zero oxidation state of Mo, complex have 18 e-1 (stable)
147
7 +6+6 -1 = 18
tropylium is a 7e- donor ligand in neutral method and +1 oxidation state
oxidation state of Mo = +1+x +0 = +1
x= 0

The above reaction is an example of 1,1-migratory insertion
38. Correct Answer (C)

Since MeTiCl3 have no electrons for back donation with л-accepting ligands like PMe3 and CO,
therefore, It reacts in order NMe3 > PMe3 > CO
Now, in (CO), Mo(thf), Mo have sufficient e-s and vacant site to react with л-acceptor ligand. Thus, the
order is CO> PMe3 > NMe3

Total valency electron 12+18=30 (A) [(OPh) in bridging donate 3 electron]
B = (n×18 - A) = 36-30=6
Metal-metal bond = B/2 = 6/2=3 Correct answer is (c)
148
A= TVE =60
B (n×18) – TVE= 72 – 60= 12
metal-metal bond= B/2 =12/2= 6
RSFRT VFW
Bond order = = = 3.5
U U

HCo(CO) 4 , HCo(CO)3PBu3 , HRh(CO)(PPh3)3 . These all are the catalyst for hydroformylation
process.

H3CoRu3(CO) 12 = 3+9+8×3+12×2 = 60 electron

149
[(H)Co6 (CO) 15] has H encapsulated.

The image shows solid state structure of HCo6(CO)15,
obtained using neutron diffraction technique. The blue
spheres are Co molecules, white spheres are CO ligands
whereas black sphere is H, encapsulated in the crystal.
Source: Journal of the Chemical Society Dalton

Transactions, Oct. 1999 (DOI: 10.1039/a810025j)

Due to increase in size of Ir, compared to Co, the Metal-Metal bond length also increases, thus the
ability to form bridge carbonyl decreases with increase in M-M bond
No of bridging CO= 3 No of bridging CO = 0

No of Terminal CO= 9 No of terminal CO =12

Explanation:
The electrophilic attack of Ph3C on the given compound, results in removal of one Methyl group from
CDMe2 ligand, thus forming an alkene. Since the reacting species is 18 electron compound, after
reaction, the final product A is also an 18e species.
150
5+8+4+1 = 18
CH→4+1=5e
X
Co(CO)3→ 9+6=15e CH Co(CO)3
But, CH₂→4+2=6e
Ni(CO)2 →10+4=14e not isolobal

In case of (c) the chances of conversion of heptacity from η5→ η3is more due to partial bond fixation.
Others will not undergo change in heptacity, to retain their aromatic properties.
IR band at 1985 cm-1 indicates terminal CO. Both P atoms are non-equivalent. Each P atom will show
doublet of doublet with (1JPRh and 2Jpp).

RT
106. Fe3(CO) 12 [Fe(CO)4] –2
8+8+2=18 electron
[Fe(CO)4] –2 is isoelectronic with Ni(CO)4
51. Correct answer (b)

151
[(η5-C5H5)(η1-C5H5)Fe(CO)2 ] → [(η5-C5H5)(η5-C5H5)Fe] ( at temp range = 221-298K)

Most commonly the metal in the complexes in their low oxidation state with d8 or d10 configuration
undergo oxidative addition.

Oxidation state of Ni in complex [Ni2(CO) 6] 2-
2x+0 = -2
x=-2/2 , x = -1
M-M bond =1

152

[Fe3(CO) 15C)]
Total valency electron= 8x5+ 15x2+4=74
PEC=TEC- n×12
PEC =74-5×12= 74-60=14
PEC/2 =14/2 = 7
7=n+2
=5+2=(n+2) Nido where n=no. of metal in electron

[η5-C5H5Rh)(C2H4)2] at -20°C shows a typical AA' XX' pattern in the olefinic region due to free
rotation of the ethylene ligand about the metal-olefin bond

Co(CO)3 15 electron
R2Si 6 electron ( not isolobal )
Mn(CO)5 17 electron
CH3 7 electron ( not isolobal )
153
Fe(CO)4 16 electron
O 6 electron ( isolobal )
Mn(CO)5 17 electron
RS 7 electron ( isolobal )

[(ηx-C6H6 )Ru(ηy-C6H6)]
x = 4, y = 6
[(η4-C6H6 )Ru(η6-C6H6)]
Total electron 4+8+6 =18 electron. (Diamagnetic complex)

∆
Ni(CO)4 + PPh3 [Ni(CO)3(PPh3)] + CO
(18 e- )
Since Ni(CO) 4 follows 18 electron rule. So, it follow substitution via dissociation mechanism i.e.
Step-1: Ni(CO) 4 →Ni(CO) 3 + CO (slow)
(18 e- )
Step-2: Ni(CO) 3 +PPh3 →Ni(CO) 3(PPh3)
(16 e- )
So, the rate of reaction depends upon the concentration of Ni(CO) 4 only because this step is slowest
step.

H3C-CH= CH2 + CO +H2 → +H3C-CH2-CH2-CHO (butanal)
in presence of Co2(CO) 8 as a catalyst
[ Hydroformylation.]
61. Correct answer is (*), none of the given option is correct .

154

Co4(CO)12
TVE =36+ 24 = 60
PEC=TVE-(nx12)=60-48=12
PEC/2=12/2 = 6 = 4+2 (n+2=Nido)

Rh(PPh3) 3Cl is a Wilkinson catalyst in hydrogenation step one PPh3 loss due to steric factor and form
Rh (PPh3)2Cl
Shape = T-shaped
So, in the product (B) it shows two signals in 1H NMR one for 5H of Cp ring and one for Fe-H
proton with intensity ratio 5: 1.

155
16 electron stable complex 18 electron stable complex

[IrCl(CO)(PPh3)2] is a 16 electron complex called as Vaska complex. Only show oxidative addition in
the presence of H2
All given options are incorrect except (a) as there is ring current disruption after formation of
complex in [(η6-C6H6)Cr(CO)3] .The shift in δ is attributed to this reason from 7.2 ppm to 4.5 almost .

The C2B9H12 is carborane anion.
C2B9H12-1 follow wade rule as
C ≡ BH
↓ ↓
(4e-) (4e-)
C2B9H12-1 ≡ (BH)2B9H12-1 ≡ B2H2B9H12-1 ≡ B11H14-1
Now, B11H14-1 is equivalent to B11H15 neutral borane which follows the formula BnHn-4
which is the general formula of nidoborane.
B11H14-1 ≡ B11H15 ≡ BnHn-4 ≡ Nido.

It is a kind of insertion reaction of M-H (metalhydride bond between CO)
156

Complex (A) HM(CO) 5 =1 + 7+ 10 =18 electron
M=Mn [7 electron]
1 + 7+ 10 =18 electron
Complex (B) [(η5-C5H5)M'(CO) 3] 2
[(η5-C5H5)Cr(CO) 3] 2 M'=Cr=6 electron
10+12+12+2 (M-M) bond = 36 electron.
70. Correct option is (c)

[Co(CO)3(NO)] NO in linear form donate (3 electron.)
↓ ↓ ↓
9 + (2x3) +3= 18 electron
[Ni(η5-Cp) (NO)]
↓ ↓ ↓
10 + 5 + 3 = 18 electron
In both complexes NO donating three electron. So, NO is in linear form.
71. Correct option is (a)

[PdCl4]-2+C2H4+H2O CH3CHO+Pd+2HC1+2Cl-
Pd(II) Pd(0)
157
2CuCl2+1/2 O2+2HCI→2CuCl2 + H2O
72. Correct option is (b)

The refluxing of RhCl3.3H,O with an excess of PPh3, in ethanol gives a complex RhCl(PPh3) 3 is
Wilkinson catalyst and common method for preparation of RhCl(PPh3) 3 is refluxing of RhCl3.3H2O
with PPh3.Moreover, on counting the total valence electrons, RhCl(PPh3) 3 = [9+3x2+1] = 16e.{Cl atom
cannot be bridging, its contribution is 1}. Wilkinson catalyst is 16e- species.
It is a square planer 16-electron complex. Valence electron counting on rhodium metal centre.
(i) there is no overall charge on complex
(ii) there is one anionic ligand (Cl-)
(iii) Rh metal atom must have +1 charge to compensate for the one negatively charged ligand. So,
the oxidation state of Rh is +1.
β-hydrogen elimination mechanism.
Since C-H, σ bond pair electron donate to the metal for this elimination. Therefore, as the donor ability
of the σ electron pair increases rate of β-elimination increases.
In option D, the unit is anti-periplanar and thus β-H elimination not possible.
For β hydride elimination reaction β hydrogen should be closer to metal in option B,C all hydrogen
atoms are far so elimination not possible (sp2 carbon)
So, more facile β-elimination occur in option (a)
158
Electron donor ability at a bond is C-H (sp³) > C-H (sp2) >C-H (sp)
So, more facile β-elimination occur in option (a)

The reaction follows SN, CB mechanism in which M-Y bond is fully broken before M-X bond begins
to form.
Thus, Id mechanism is the most evidential mechanism.

[B12H12] 2- ≡ [BnHn] 2-
Therefore, it is closo structure

SbCl3+3EtMgBr→SbEt3 +3MgBrCl
2SbEt3+SbI3→ [Sb(Et)I2]n +SbEt2I

159
Due to this agostic interaction C-H bond becomes weak and hydrogen flanked in between M and C.As
proton come in contact with metal becomes shielded and upfield shift in 1H NMR.
Since v ∝ 𝐾 ,bond strength of C-H bond decreases, in IR spectrum shift to lower wave number.

Suzuki coupling-Palladium catalyzed cross coupling between organoboranic acid and halides.
Heck coupling-Palladium catalyzed C-C coupling between aryl halides or vinyl halides and activated
alkenes in the presence of a base.
Sonogashira coupling-This coupling terminal alkynes with aryl or vinyl halides is performed with a
palladium catalyst, Cu(I) cocatalyst and amine base.
Negeshi coupling-This reaction is the organic reaction of an organohalide with an organic-zinc
compound Pd and Ni catalyst.

Here, Cp is cyclopentadienyl ligand is one of the most common and popular ligands in organometallic
chemistry.
It is an anionic ligand that normally coordinates in an η5 mode as a 6 electron donor.

Now, 18-electron rule apply on the complexes
160
[Mn(η5-Cp)(CO) 3] does not follow 18-electron rule. So, this complex is most deshielded compound
when we are going 3d to 4d and 4d to 5d series in the transition element the shielding effect decrease
because of the electron density or the distance between metal to ligand, increases. So, [Fe(η5-Cp)2] is
more shielded than other.
Thus, the compound D is most shielded and compound A is most deshielded.
[Ru6(C)(CO)17]
TEC =8x6+4+17x2 = 86
PEC= 86 - 6x12 = 14
PEC/2= 14/2 = 7
Therefore, 7=6+1=(n+1) closo
[Os5(C)(CO)15]
TEC= 8x5+4 +15x2 = 74
PEC =74-12x5
PEC = 74-60= 14/2 =7= (5+2)=(n+2) .Therefore, nido
[Ru5(C)(CO) 16]
TEC= 8x5+4+16×2
161
TEC=76
PEC =76-60=16
PEC/2=16/2 =8= (5+3)=(n+3) Arachno

For reductive elimination, the eliminating group should be electron releasing group and also the
eliminating product should be neutral.So, only Me group is electron releasing group among all the given
option.
83. Correct option is (C)
All the products are possible but possibility of (4) is least as alkene doesnot undergo reductive
elimination reaction easily as compare to alkane.
84. Correct option is (d)

alkyne can act as a 2 or 4electron donor .
Step-1 (ϭ -bond formed)
L(π)→ M(ϭ)
From filled acetylene π orbitals to empty metal d orbital
162
Step-2 (π -bond formed)

M(π)→ L(π*)
From filled metal d orbital to empty acetylene π* orbitals
Correct option is (d)

[W(η5-C5H5)(𝝁-Cl)(CO) 2] 2
TVE(A)= (6+5+3+4)×2=36
B = nx18-A = 2×18-36=0
Hence, number of M-M= B/2=0/2 =0
Example of migratory insertion reaction in which alkyl group insert to CO. A new ligand create acycl a
vaccancy is created which is occupied by new ligand.

163
Hc = central proton
Ha= is anti with respect to Hc
Hs= syn with respect to Hc
Ha , Hs , Hc environment are different new intensity ratio 2: 2 :1. When allyl is non-fluxional.

C2B5H7 C ≡ BH
(BH)2 B5H7 ≡B7H9 ≡ (B7H7)-2, (closo)
(BnHn -2)

Structure of Uranocene
Hence, oxidation state of U=+4

Thus in uranocene U is in +4 oxidation state and have cyclooctatetraenide ligand.

-
[V (Co) 6] →[V(CO) 6] ( in presence of H3PO4)
-
[Co(CO)4] → [HCo(CO)4] ( in presence of H3PO4)
164

Number of electron involving in metal cluster = T.V.E - 12
T.V.E in Ru(CO) 3 = 8 + 6 = 14 (T.V.E = total valence electron)
Hence, number of electron provided for cluster bonding = 14-12=2
On photolysis of Z first a 16 electron intermediate is formed which is option B, and for final product
allyl attains maximum heptacity therefore η1 allyl is converted η3 allyl which is option D

Mechanism

165
-1
Terminal CO=2120-1850 cm
-1
µ2 CO=1850-1750 cm
2
In this complex M-M bond order = 1 and two types of CO's terminal as well as -bridging. So,
νco band lies in both range.

Explanation:

166
Explanation

B-H= 4e- fragment isolobal fragment should have 14 electron.
Cp + Co=5+9=14 e-

TVE= 9×2 + 8×2 + 2×11 + (4×2)
TVE = 18+ 16+ 22+8 = 64 = A

B = (n ×18) –A = (4×18) – 64 = 72-64 =8
Number of metal-metal bond = B/2=8/2 = 4

Structure of CoF2 =
due to more space requirement for double bond the bond angle ∠F-C-O will be higher that of ∠F-C-F
and also C-O bond order is larger than C-F hence, C-O bond length will be smaller than C-F.
As the electron goes to e*1g (dxz , dyz), orbital of metallocene bond length increases as they are
anologous eg set orbital of an octahedral complex
167
Thus, in Ni(Cp)2 there are highest number of electrons in e*1g . Hence, it has highest M-C bond
length.
Ni(Cp)2 > Co(Cp)2 > Fe(Cp)2
Therefore, total protons 8, but in η4-mode COT attached to the four carbon and 4 protons show different
environment at -140°C because fluxonial behaviour slow down and hence , 4 signals will be observed.

C2B3H5 = (B-H)2B3H5 = B5H7
Each B-H unit give 2 electron. For cage bonding.
168
Hence, 5(B-H)= 5x2= 10 electron. Each hydrogen one electron,

Hence, 2H=2x1= 2 electron
Total =12 electrons
C2B4H6 = (BH)2B4H6 =B6H8
6(B-H) 6x2=12e-
2H= 2x1=2e-
Total = 14 electron
B5H9
5(B-H)=5x2=10
4H = 4x1= 4
Total =14 e-

During fluxional axial ligands are exchanged with equatorial ligand. Hence,

169

TVE = 10+12+12=34= A.
B= (n×18) -A
B=(2×18)-34 = 36-34=2
Number of metal-metal bond =2/2=1
On heating :
TVE 10+12+8 = 30 =A
B=(n×18)-A= 36-30=6
Number of metal-metal bond = B/2=6/2 =3
170

T.V.E. = 8 x 2 + 5 x 2 +2 x 2 + 4= 34 = A
B = (nx18)-A=36-34= 2
Number of M-M bonds=B/2=2/2=1
3-bridging, 1-M-M bonds.

When the norbornene is strained molecule because the hybridization is sp2 when the metal attached with
norbornene back-bonding takes place and due to this back-bonding the hybridization changes to sp2-sp3
and hence relief to strain

Statement I →[Rh(CO)2 I2]-
Converts CH-I and CO into CH3COI
Statement → [Rh(CO)2 I2]- is diamagnetic in nature.
I and II are correct but II is not correct explanation of I.
171
Correct explanation: Monsanto process occurs via oxidative reaction, migratory insertion and re ductive
elimination reaction for that the starting compound must be square planar.
111. Correct option is (a) & (c)

[ReH9]-2 → Tricapped trigonal prismatic
Atoms 1 to 6 are the prism atoms, 7 to 9 are H-atom are equatorial hydrogen.

Co(CO)3
9+6 =15 (for 18 electron require 3 electron)
P ↔ BH₂
5 3+2 = 5 (for 8 electron require 3 electron)
CH ↔ BH2 (for 8 electron require 3 electron)
4+1=5 3+2=5
Ni(η5- C5H5) (for 18 electron require 3 electron)
10+5=15
Co(CO)3 ↔ P ↔ CH ↔ Ni(η5- C5H5)

[Co(η5- C5H5)B4H8]
Co(η5- C5H5) ↔ BH
14 4
172
[BHB4H8] = [B5H5]-4 = [BnHn]-4→nido

[Mn(η2-B3H8)(CO)4]
[Mn(CO)4] ↔ [BH2]
7+8=15 5
[ B3H8BH2 ] = [B4H10] = [B4H4]-6 = [BnHn]-6 → Arachno

[Rh6C(CO)15]-2
TVE = 9x6 + 4 + 15x2 +2 =54+4+2+30 = 90
Hence, it has trigonal prism geometry.

Compound (C) shows four 1H NMR signal

173
The species having same number of electrons are called isoelectronic.

A =[V(CO)6]=5+12=17e-
B =[Cu(η5- C5H5)(CO) ]=11+5+2=18e-
C =[Co(CO)4]-1 =9+8+1=18e-
D=[IrCl(CO)(PPh3)2] = 9+1+2+4=16e-
Therefore B and D are isoelectronic species .
Two fragments are isolobal if the number, symmetry properties, approximate energy and shape of their
frontier molecular orbitals and the number of electrons in them are similar not identical but similar.
CH3+ = 4+3-1 = 6 ;
[Cr(CO)5]=6+10=16
Na [Mn(CO)5] + CH₂=CH-CH₂-Cl →
Mechanism:

[B6H6]-2 has 6 + 1 = 7 bonding molecular orbital
[B6H6]-2 = B-H=2x6=12 e-
for 2 negative charge, hence 12e- +2e- =14e-

174
[(η5-Cp) Fe (η6-C6H6)]+

In [Fe(S2CNEt2)3] , oxidation state of Fe = +3

In trigonal prismatic ligand field, energy of 'd' orbital is
dyz = dxz > dz2> d x2-y2 = dxy
Hence, the most stablized 'd' orbital is dxy

Number of valence electron in CH2 = 6
Hence, fragment having 16 electron will be isolobal to this fragment.
A→ CpCr(CO)2 = 5+6+4=15
175
B→CpCu = 5+11=16
C→Ni(CO)2 = 10+4=14
D→ Cr(CO)4 = 6+8 = 14
E→Fe(CO)4 = 8+8=16

According to reductive elimination reaction mechanism cis-complex can give the product but trans-
complex is not suitable for reaction and does not give reductive elimination product. Since, ligand given
in option (d) forms a trans-complex with Pd(II) due to the presence of flexible methylene (-CH2-)
groups. Therefore, reductive elimination not occured.
Actually formed but does not give reaction This can give reaction but not formed

Sn9-4 = 9×4+4=40 , thus it follow 4n+4. Hence, it has nido structure

176
Compound [V(CO)6]- [Cr(CO)6] [Mn(CO)6]+ H3B.CO

ῡco - cm-1 1860 2000 2098 2164
[V(CO)6]- < [Cr(CO)6] < [Mn(CO)6]+ < H3B.CO
Order of ῡco streching frequency
[V(CO)6]- > [Cr(CO)6] > [Mn(CO)6]+ >H3B.CO

Order of C-O bond length

The insertion of carbon monoxide into a metal carbon bond to form an acyl group is the basis of
carbonylation reaction.
Intermediate
Donation of π-electron of the C=C to an empty ϭ orbital of the metal accompanied by back donation
from a filled metal d π orbital into an empty C=C π* orbital
(Synergic bonding ∝ C-C bond length)

(A) [{Co(η5-C5H5)}2(C2B6H8)]
177
[{Co(η5-C5H5)}2]→18+10=28 is isolobal with (B7H7)

[(BH)7 (BH)2 B6H8]
B15H17 → B15H15-2→ closo
(B) [B4C2H8] →[(BH)2B4H8]→B6H10 or B6H6-4 →nido
(C) [B10H13 {(Au(PPh3)}]
Au(PPh3)→11+2=13 is isolobal with B3H4
[B13H₁7]→ B13H13-4 →nido
(D) [C2B8H10] →(BH)2B8H10 →B10H12 →B10H10-2 → closo

[Pd(PPh3)4] and Ni(CO)4 compounds are isoelectronic (follow 18 electron rule) and isotructural in
natural (tetrahedral structure)
[Pd(PPh3)4] = 10+8=18e-
[Ni(CO)4] = 10+8=18e-

178
18 e- (A) (18e -) (B) (18e-)

Two signals with three signal with 3:5:15
3:5 intensity ratio intensity ratio

[ReCl8]-2 =2Re+3 (d4 ) + 8Cl-
δ -bond: Eclipsed geometry
[Os2 Cl8]-2 has Os+3 d5
Bond order =3: staggered

In Wacker process, a Co catalyst CuCl2 which could re-oxidise Pd(0) back to Pd(II)
[PdCl4]-2 +C2H4 +H2O → CH3CHO+ Pd+ 2HCl+2Cl-
Pd + 2CuCl2 + 2Cl-→[PdCl4]-2 +2CuCl
2CuCl + ½ O2 + 2HCl →→2CuCl2 + H2O
C2H4+1/2 O2 →CH3CHO

As the electronegativity of X in PX3 increases, π-acceptor tendency increases.
PF3 > P(OPh)3 > PPh3 > PMe3
179
In BH3.CO formation CO interact with vacant p-orbital, whereas electron is donated by antibonding
orbital of CO due to which bond order increases and νCO increases.

Complex:
Mo(PF3)3(CO)3 →2055, 2090
Mo{P(OMe3)3}(CO)3 →1888, 1977
Mo(PPh3)3(CO)3 →1835, 1934
Mo(pyridine)3(CO)3→ 1746, 1888
π-acceptor tendency of spectator ligand is PF3 > POMe3 > PPh3 > Pyridine. Therefore, PF3 reduce more
electron density from the metal in complex to pyridine consequently. As the electron density on metal
decreases, M-C bond strength decreases, C-O bond strength increases. Hence, vCO increases,

VCN = [Fe(CN)6]-3 > [Fe(CN)6]-4
Vco=[Cr(CO)6] > [Cr(CO)3(NH3)3]

180
[Rh9P(CO)21]-2 → TEC = 9×9+5+2×21+2=130

PEC=130 - 9×12=22
PEC/2 = 22/2 =11→ 9+2=(n+2)=nido
Bite angle 850 910 >1200 960

The linear and branched formylated product is depends upon natural bite angle of biphosphines. As the
natural bite angle increases selectivity for linear product increases.

Ni = 10
Cp= 5e-
Ph2P=3e-
TOTAL = 18e
Therefore, No M-M bonds
181
Electron withdrawing group present on the metal decreases the electron density and hence decreases the
rate of oxidative addition because the rate of oxidative addition is directly proportional to the electron
density on the metal.

Fe(-1)→ d9 system
0
d9 ML3 CH
For d9 –ML3, original co-ordination number will be considered as ML6.
Therefore, [Fe(CO)2(PPh3)]- having three co-ordination number, missing three from original ML6 and
similarly for CH, three ligands also missing from original CH4 . Hence, [Fe(CO)2(PPh3)]- is isolobal
with CH but not with CH2+ (5e-) because two ligands missing from original CH4.

[Ru6C(CO)17]
TEC = 8x6+4+17×2=86
PEC= TEC- n x 12.
PEC= 86- 6x12
182
PEC= 86 - 72=14
PEC/2 = 14/2=7 (n+1) => Closo
In the cluster [Ru6C(CO)17]the carbon atom is encapsulated at cavity of cluster and equally interacted
with all Ru centres.
For reaction A:
183
For Reaction B:
For reaction C:
Two ligands are present on z-axis therefore, dz² -orbital is involved in ϭ bonding. Also three ligands are
present in xy plane, therefore, d x2-y2 and dxy orbitals are involved in ϭ -bonding. Thus the d x2-y2 and
dxy orbitals remain nonbonding.

184
The number of CO bands in fac-[Mo (PPh3)3(CO)3] =2

The number of CO bands in trans-[Mo(PPh3)2(CO)4]= 1

In aqueous medium, the most stable vanadium species is hydrated vanadyl ion [VO]+2 i.e
[VO(H2O)5]+2

Cp2Fe
10e- +8e- = 18 e-
Number of electron in anti-bonding orbital = 0
Cp2Co
10e- +9e- = 19e-
Cp2Ni
10e- +10e- = 20e-
As the number of electron present in the anti-bonding orbital increases , M-ligand bond becomes weak
and hence, bond length increases. Therefore, the correct order of M-C distance is
Cp2Ni > Cp2Co > Cp2Fe

This step is the slowest step and hence rate determining step.
185

[Fe5(CO)14N]-
TEC= (8x5) + (14×2)+5+1 = 40+28+6 =74
PEC =74-(12x5)=14
PEC/2= 14/2 =7 ie.n+2
Thus, it is a nido cluster.
[Co6(CO)13N]-
TEC= (9x6) + (13x2)+5+1 = 54+26+6 = 86
PEC=86 - (6x12) = 14
PEC/2=14/2 = 7 i.e n+1
Thus, it is a closo cluster.
157. As per DMG rule , the rate of nucleophilic addition is :

186
Square planar complexes undergo associative pathway. So, ligand substitution process can be better
understood in terms of crystal field activation energy (CFAE). Considering trigonal bipyramid or square
pyramidal geometry in Transition state (T.S.), C.F.A.E. can be calculated.
C.F.A.E. (Dq) = C.F.S.E. (Dq) of T.S - C.F.S.E. (Dq) of square planar complex.
The Dq value increases of the heavier congeners and it makes heavier congeners more inert. So rate of
substitution will be
Ni(II)> Pd(II)> Pt(II)

The highest rate of substitution of a CO ligand on heating with PPh3 is easy where slippage of haptacity
is easy.
For
slippage is easy because it is not at the cost of aromatic character (η5 → η3).
But η5 – Cp* , complexes, rate decreases because with respect Cp slippage of haptacity is due to at the
cost of aromatic character.
Due to high field strength of Cp* , it forms low spin complexe and having
one unpaired electron
Cp2*Mn = 2Cp* =10e- and Mn = 7e- =17e-
187
12e electrons are in the lower orbitals and remaining five electrons occupies the orbital as follows.
Electronic Configuration = e2g4 a1g1

Taking 18 valence electron as guide, the products will be predicted.
∆
[Mo(N2)2(PMe2Ph)4] [(η6-PhPMe2)Mo(PMe2Ph)3] + N2
18 V.E 18 V.E
∆
[ReCl(N2)(PMe2Ph)4] + N2
18 V.E 18 V.E 18 V.E
(Cl as a bridging ligand)

[Fe4C(CO)12]-2
Polyhedron electron count = T.E.C.-12 x n = [4 x 8 + 4 + 24 + 2] -12x4 = 62 – 48 = 14
Hence, x= PEC/2 = 14/2 = 7 = n+3 i.e arachno
T.E.C.= 62
So, it adapts the butterfly structure expected for arachno

Mechanism
188
Protonation of ferrocene with strong acids results intermediate through exo-attack

At +30°C , the compound shows structural fluxionality.
Structural fluxionality
So, the two Cp rings display the different bonding modes ϭ(η1) and π (η5).
At room temperature (30°C) observed doublet due to η5-Cp and η1-Cp
but at -80°C, four peaks observed.
5: 2 : 2 : 1
↓ ↓ ↓ ↓
H6-10 H2-3 H4-5 H1

The product (A) shows three strong bands at 1986, 1935 and 1601 cm-1.
Three different IR bands suggest, the different CO environment in the complex.
For compound
189
three different -C≡O environments are present.

Terminal -C≡O , ῡ-C≡O (terminal) →2120-1850 cm and M-C(=O)-CH3 ῡ-CO =1700-1600 cm-1
compound (b) and compound (c) show two and four different C≡O environments.

In bent mode NO donates one electron to metal centre, thus statement A is incorrect.
IR range for bent NO is 1525 − 1690 𝑐𝑚FW whereas for linear NO it is 1690 − 1900 𝑐𝑚FW . Thus
statement B is correct.
Electronic configuration for CO is,
Electronic configuration for NO is,

Thus statement C is also correct.
167. Correct option (c)

Statement A is correct, as in order to form pi bond between metal and carbine, 2 electrons are donated.
Statement B is incorrect, the given carbene is Fischer carbene and it is electrophilic in nature.
Statement C is correct, rotation around the Cr=c(OME)Me double bond has low barrier.
168. Correct option (d)

TVE for 𝑅𝑢{ (𝐶𝑂)W~ 𝐵 F is 86
TVE for 𝑂𝑠{ (𝐶𝑂)WV 𝑃 F is 90
TVE for [𝑂𝑠‚ (𝐶𝑂)W{ ] is 64
Following the below table,

S.No Total Valence Electrons Cluster Framework
1 64 Square
2 86 Octahedral
3 90 Trigonal Prismatic
190

In option (b) both Fe follows 18e rule.
Fe = 8e
Cp = 5e
Linear NO = 3
Bridging CO = 2
Total 18e, hence, thermodynamically stable.

The given reaction is example of Kumada coupling between Pd and Mg

Carbene whether it is singlet or triplet, they are bent in configuration.
In the presence of +M groups (which is chlorine here), the carbine will be singlet.
1

192
Main Group Elements
[CSIR JUNE 2011]
1. The correct order of stability of difluorides is:

(a) GeF2 > SiF2 > CF2
(b) CF2 > SiF2 > GeF2
(c) SiF2 > GeF2 > CF2
(d) CF2 > GeF2 > SiF2
2. Alkali metal superoxides are obtained by the reaction of

(a) Oxygen with alkali metals in liquid ammonia.
(b) Water with alkali metals in liquid ammonia
(c) H2O2 with alkali metals.
(d) H2O2 with alkali metals in liquid ammonia.
3. Match List-I (compounds) with List-II (application) and select the correct answer using the codes given
below the lists.
List 1 List 2
(A) Tri sodium phosphate (i) Plasticizer
(B) Tri aryl phosphates (ii) Water softener
(C) Tri ethyl phosphate (iii) Toothpaste
(D) Calcium hydrogen phosphate (iv) Insecticides
(a) (A)-ii (B)-i (C)-iv (D)-iii

(b) (A)-i (B)-ii (C)-iv (D)-iii
(c) (A)ii- (B)-iii (C)-iv (D)-i
(d) (A)-iii (B)-i (C)-ii (D)-iv
Q4 Among the following, the number of anhydrides of acids are

CO, NO, N2O3 , B2O3 , N2O5 , SO3 and P4O10
(a) 3
(b) 4
(c) 5
(d) 6
[CSIR DEC 2011]
5. The correct statement regarding closo-{BnHn} species is:

193
Main Group Elements
(a) it always has-2 charge
(b) it always has +2 charge.
(c) it is a neutral species
(d) it is more reactive than nido , arachno, and hypo-boranes
6. Lewis acidity of BCl3, BPh3 and BMe3 with respect to pyridine follows the order
(a)BCl3> BPh3> BMe3
(b)BMe3 > BPh3 > BCl3
(c)BPh3 >BMe3 > BCl3
(d)BCl3 >BMe3 > BPh3
7. Among the following pairs

(1) oxygen-sulfur
(2) nitrogen -phosphorus
(3) phosphorus arsenic
(4) chlorine- iodine
Those in which the first ionization energies differ by more than 300 kJ mole are:
(a) (1) and (3) only
(b) (1) and (2) only
(c) (2) and (3) only
(d) (3) and (4) only
8. The reaction between NH4Br and Na metal in liquid ammonia (solvent) results in the products
(a) NaBr, HBr
(b) NaBr, H₂
(c) H2, HBr
(d) HBr, H₂
9. The material that exhibits the highest electrical conductivity among the following sulfur - nitrogen
compounds is
(a) S4N4
(b) S7NH
(c) S2N2
(d) (SN) x
10.The final product (s) of the reaction P(OR)3 +R'X is/are

(a) R'PO(OR)2 and RX
(b) [R'PO(OR)2]X
(c) [R'RPO2(OR)]X
(d) RORʹand P(OR)2X
11. A Sodalite cage in zeolites is

(a) a truncated tetrahedron
(b) an icosahedron
(c) a truncated octahedron
(d) a dodecahedron
194
Main Group Elements
12. The styx code of B4H10 is:

(a) 4120
(b) 4220
(c) 4012
(d) 3203
13. Bayer's process involves.

(a) Synthesis of B2H6 from NaBH4
(b) Synthesis of NaBH4 from borax
(c) Synthesis of NaBH4 from B2H6
(d) Synthesis of B3N3H6 from B2H6
[CSIR JUNE 2012]
14 The correct structure of beryllium nitrate is :
(a)
(b)
195
Main Group Elements
(c)
(d)
15. The strength of pπ-dπ bonding in E-O (E = Si, P, S and CI) follows the order
(a) Si-O>P-O>S-O>Cl-O
(b) P-O>Si-O>S-O>Cl-O
(c) S-O>Cl-O>P-O>Si-O
(d) Cl-O>S-O>P-O>Si-O
16. Among the halides, NCl3 (A), PCl3 (B) and AsCl3 (C), those which produce two different acids.
(a) A and B
(b) A and C
(c) B and C
(d) A, B and C
17. The most used acid catalyst in oil industry and the relevant process are respectively
(a) Alumino phosphate and reforming
(b) Alumino silicate and cracking
(c) Alumino silicate and reforming
(d) Alumino phosphate and cracking.
18. The correct structure of P4S3 is:

196
Main Group Elements
(a)
(b)
(c)
(d)
19. Low oxidation state complexes are often air-sensitive, but are rarely water sensitive because
(a) Air is reducing in nature while water is inert
(b) Both air and water are oxidizing in nature
(c) Both air and water are not acceptors
(d) Complexes with low oxidation states will easily lose electrons to O2 but will not bind to a π–donor
molecule like H2O.
[CSIR DEC 2012]
20. For the deposition of Pb by electroplating, the best suited compound among the following is
(a) PbCl2
(b) PbSO4
(c) Pb(Et)4
(d) Pb(BF4)2
21. The electronegativity differences is the highest for the pair

(a) Li, Cl
(b) K, F
(c) Na, Cl
(d) Li, F
22. Structure of a carborane with formula, C2B4H8 , is formally derived from

(a) Closo-borane
(b) Nido-borane
(c) Arachno-borane
(d) Conjuncto-borane
197
Main Group Elements
23.Boric acid is a weak acid in aqueous solution. But its acidity increases significantly in the presence of
ethylene glycol, because
(a) ethylene glycol releases additional H+
(b) B(OH)4- is consumed in forming a compound with ethylene glycol.
(c) ethylene glycol neutralizes H+ released by boric acid.
(d) Boric acid dissociates better in the mixed-solvent.
24. Silicates with continuous 3D frame work are

(a) Neso-silicates
(b) Soro-silicates
(c) Phyllo-silicates
(d) Tecto-silicates
[ CSIR JUNE 2013]
25. Which of the following pairs has the highest difference in their first ionization energy?
(a) Xe, Cs
(b) Kr, Rb
(c) Ar, K
d) Ne, Na
26. Which of the following is used as propellant for whipping creams?

(a) N₂O
(b) NO
(c) N2O3
(d) N2O5
27.Flame proof fabrices contain

(a) H₂NC(O)NH2.Na2SO4
(b) H2NC(S)NH2.Na2SO4
(c) H2NC(O)NH2.H3PO4
(d) H2NC(S)NH2.H3PO4
28. Among the oxides of nitrogen, N2O3 , N2O4 ,and N2O5 the compound(s) having N-N bond is/are
(a) N2O4 and N2O5
(b) N2O3 and N2O5
(c) N2O3 and N2O4
(d) N2O5 only
29. Identify the pairs in which the covalent radii of elements are almost similar
(A) Nb, Ta
(B) Mo, W
198
Main Group Elements
(C) La, Lu
(D) Sc, Y
(a) A and B only
(b) A and C only
(c) B and C only
(d) A, B and C only
30. The correct equilibrium order for the interconversion of different forms of SiO2 is
(a) Tridymite ↔ quartz ↔cristobalite ↔ liquid SiO2
(b) quartz ↔Tridymite ↔cristobalite ↔liquid SiO2
(c) quartz↔cristobalite ↔ tridymite↔liquid SiO2
(d) cristobalite ↔ tridymite ↔ quartz ↔liquid SiO₂
[CSIR DEC 2013]
31. The reaction of FeCl3.6H2O with SOCl2 yields.

(a) FeCl2 (s), SO2 (g) and HCl (g)
(b) FeCl3(s), SO2(g) and HCI(l)
(c) FeCl2 (S), SO2(s) and HCl (g)
(d) FeCl3(s), SO2(g) and HCl(g)
32. Among the molten alkali metals, the example of an immiscible pair (in all proportions)is
(a) K and Na
(b) K and Cs
(c) Li and Cs
(d) Rb and Cs
33. Treatment of ClF3 with SbF5 leads to the formation of a/an

(a) polymeric material
(b) covalent cluster
(c) ionic compound
(d) lewis acid-base adduct
34. The reason for the chemical inertness of gaseous nitrogen at room temperature is best given
(a) high bonding energy only
(b) electronic configuration
(c) HOMO-LUMO gap only
(d) high bond energy and HOMO-LUMO gap.
35. Commonly used scintillator for measuring radiation is

(a) Nal(AI)
(b) Nal(TI)
(c) CsI(TI)
199
Main Group Elements
(d) Csl(AI)
36. Two tautomeric forms of phosphorus acid are
(a)
(b)
(c)
(d)
37. The solid state structure of aluminum fluoride is
(a)
(b)
(c)
(d)
38. The orbital interactions shown below represent

200
Main Group Elements
(a) CH-Al interactions in Al2 (CH3) 6

(b) B-H interactions in B2H6
(c) CH-Li interaction in Li4(CH3) 4
(d) CH3CH2-Mg interactions in EtMgBr.(OEt2) 2
39. In a specific reaction, hexachlorocyclotriphosphazene, N3P3Cl6 was reacted with a metal fluoride to
obtain mixed halo derivatives namely N3P3Cl3F (A), N3P3Cl4F (B), N3P3Cl3F3(C), N3P3Cl2F4
(D),N3P3ClF5 (E). Compositions among these which can give isomeric products are
(a) A, B and C
(b) B, C and D
(c) C, D and E
(d) E, A and B
40. Xenon forms several fluorides and oxofluorides which exihibit acidic behaviour. The correct sequence
of descending Lewis acidity among the given species is represented by
(a) XeF6 > XeOF4 > XeF4 > XeO2F2
(b) XeOF4 > XeO2F2 > XeOF4 > XeF6
(c) XeF4 > XeO2F2 > XeOF4 > XeF6
(d) XeF4> XeF6> XeOF4 > XeO2F2
41. Number of isomeric derivatives possible for the neutral closo-carborane, C2B10H12 is
(a) three
(b) two
(c) four
(d) six
42.For higher boranes 3c-2e 'BBB' bond may be a part of their structures. In B5H9, the number of such
electron deficient bond(s) present is/are
(a) four
(b) two
(c) zero
(d) one
201
Main Group Elements
[CSIR JUNE 2014]
43. Reactions of elemental as with hot and conc. HNO3, and H2SO4 respectively, give
(a) As4O6 and As2(SO4)3
(b) As(NO3)5 and As2(SO)3
(c) As4O6 and H3AsO4
(d) H3AsO4 and As4O6
44.Chromite ore on fusion with sodium carbonate gives

(a) Na2CrO4 and Fe2O3
(b) Na2Cr2O7 and Fe2O3
(c) Cr2 (CO3)3 and Fe(OH)3
(d) Na2CrO4 and Fe2(CO3)3
45. The correct order of decreasing electronegativity of the following atoms is,
(a) As > Al> Ca >S
(b) S> As > Al> Ca
(c) Al> Ca >S>As
(d) S> Ca >As > Al
46. The correct order of the size of S, S2-, S2+ and S4+ species is,
(a) S > S2+> S4+ > S2-
(b) S2+ >S4+ > S2- > S
(c) S2-> S > S2+ > S4+
(d) S4+ > S2- > S > S2+
[CSIR DEC 2014]
47. The reaction between SbF5 and two equivalents of HF leads to the formation of
(a) H2SbF3+2F2
(b) HSbF2 + 3F2
(c) SbF3+H2 +2F2
(d) [SbF6] - [H2F] +
48. Among F-, Na+, O2- and Mg2+ ions, those having the highest and the lowest ionic radii respectively are
(a) O2- and Na+
(b) F- and Mg2+
(c) O2- and Mg2+
(d) Mg2+ and O2-
49.The reaction between diphenyldichlorosilane and water in 1:2 molar ratio gives product A which on
heating above 100°C yields a cyclic or polymeric product B. The products A and B respectively, are
202
Main Group Elements
(a)
(b)
(c)
(d)
11
50. A borane (X) is reacted with ammonia to give a salt of borohydride (Y). The B NMR spectrum of Y
consists of a triplet and a quintet. The borane X is
(a) B2H6
(b) B3H9
(c) B4H8
(d) B5H9
51. 12-Crown-4 binds with the alkali metal ions in the following order :
Li+ >> Na + > K+ >Cs+ . It is due to the
(a) Right size of cation crown ether
(b) Change in entropy being positive
(c) Conformational flexibility of crown ether
(d) Hydrophobicity of crown ether
52. The main products of the reaction of equimolar quantities of XeF6 with NaNO3 are
(a) XeOF4 , NaF and NO2F
(b) XeO2F2, NaF, NOF and F2
(c) XeOF4, NaNO2 and F2
(d) XeF4, NaNO2, and F2O
[CSIR JUNE 15]
53. All forms of phosphorus upon melting, exist as
(a)
(b)
203
Main Group Elements
(c)
(d)
54. The correct set of pseudo halide anions is

(a) CN- , ClO4-, BF4-, PF6-
(c) SCN-, PO-34, H2PO-4 ,N-3
(b) N-3, NO-3, HSO4 AsF-6
(d) CN-, N-3 , SCN-, NCN2-
55. The oxoacid of phosphorus having P atoms in +4, +3, and +4 oxidation states respectively, is
(a) H5P3O10
(b) H5P3O7
(c) H5P3O8
(d) H5P3O9
56. Considering the inert pair effect on lead, the most probable structure of PbR2 [R =2.6-C6H3 (2. 6 –
Pr2C6H3)2 is
(a)
(b)
(c)
(d)
[CSIR DEC 2015]
57. The order of increasing Bronsted acidity for boron hydrides is

(a) B5H9 <B6H10 <B10H14
(b) B10H14 <B5H9 <B6H10
(c) B6H10 <B10H14 <B5H9
204
Main Group Elements
(d) B10H14 <B6H10 <B5H9
58. The ring size and the number of linked tetrahedral present in [Si6O18] -12 are, respectively
(a) 6 and 6
(b) 12 and 6
(c) 12 and 12
(d) 6 and 12
59. Consider the following reaction :

N3P3Cl6 + 6HNMe2 →N3P3Cl3(NMe2)3 +3 Me₂NH.HCI
[A]
The number of possible isomers for [A] is
(a) 4
(b) 3
(c) 2
(d) 5
60. The reaction of BCl3 , with NH4Cl gives product A which upon reduction by NaBH4 gives product B.
Product B upon reacting with HCI affords compound C, which is
(a) Cl3B3N3H9
(b) [ClBNH] 3
(c) [HBNH] 3
(d) (ClH)3B3N3(ClH)3
61. Protonated form of ZSM-5 catalyzes the reaction of ethene with benzene to produce ethylbenzene.
The correct statement for this catalytic process is
(a) alkyl carbocation is formed
(b) carbanion is formed
(c) benzene converted to (C6H5) + group
(d) vinyl radical is formed
[CSIR June 2016]

62. The numbers of P-S and P-P bonds in the compound P4S3 are, respectively
(a) 6 and 3
(b) 4 and 3
(c) 3 and 6
(d) 6 and 2
63. The compound which dissolves in POCl3 to give a solution with highest chloride ion concentration ,is -
(a) Et3N
(b) KCl
(c) FeCl3
(d) SbCl5
205
Main Group Elements
[CSIR Dec 2016]
64. The metal iodide with metallic lustre and high electrical conductivity is
(a) NaI
(b) CdI2
(c) LaI2
(d) BiI3
65. Consider the following statements for KC8:

(A) It is paramagnetic
(B) It has eclipsed layer structure
(C) Its electrical conductivity is greater than that of graphite.
(a) A and B
(b) A and C
(c) B and C
(d) A, B and C
66. Among the following, choose the correct products that are formed in the reaction of S2 Cl2 with
ammonia in CCl4
NH4Cl(A) , S4N4 (B) , S8 (C) , and S3N3Cl3 (D).
(a) A, B and C
(b) A, B and D
(c) B, C and D
(d) A, C and D
67. The final product(s) of the reaction of arachno borane, B4H10 with NMe3 is/are
(a) [BH3.NMe,] and [B3H7 . NMe3]
(b) [BH2(NMe3)2]+ [B3H8]-
(c) [B4H10.NMe3]
(d) [B4H10.NMe3] and [BH2(NMe3)2]+ [B3H8]-
[CSIR JUNE 2017]
68. Both potassium and sulfuric acid form intercalation compounds with graphite. The graphite layers
are
(a) reduced in both the cases
(b) oxidized in both the cases
(c) oxidized in the case of potassium and reduced in the case of sulphuric acid
(d) reduced in the case of potassium and oxidized in the case of sulphuric acid
69. Addition of two electrons to the bismuth cluster Bi5+3 results in a change of structure type from
(a) closo to nido
(b) nido to arachno
(c) closo to arachno
(d) arachno to hypho
206
Main Group Elements
70. The compound N2F2 has two isomers. Choose the correct option from the following:
(a) both isomers possess a ϭv plane
(b) both isomers possess ϭh plane
(c) one isomer has a ϭh plane while the other has a ϭv plane
(d) none of them have a ϭh plane
[CSIR DEC 2017]
71. The first ionization energy is the lowest for

(a) Br
(b) Se
(c) P
(d) As
72. Choose the incorrect statement for the phosphomolybdate anion [PMO12O40]-3
(a) It has a Keggin structure.
(b) Phosphorus is in +5 oxidation state.
(c) It is extremely basic.
(d) It forms crystalline precipitates with [R4N]+ (R = bulky alkyl or aryl group)
[CSIR JUNE 2018]
73. The structure of CaB6 is close to that of

1. Cesium chloride
2. Nickel arsenide
3. Rock salt
4. Zinc blende
74. Among the elements Zn, Ga, Ge as As, the one with the lowest first ionization energy is -
1. As
2. Zn
3. Ga
4. Ge
75. A binary fluoride (Z) of xenon combines with two moles of NaF to give a product which on hearting to
100°C affords compounds A. the alkaline hydrolysis of A gives perxenate salt. Z and A are, respectively,
1. XeF2 and XeF4
2. XeF4 and XeF6
3. XeF6 and XeF4
4. XeF6 and XeF6
76. Consider following statements:

I: AsCl5 is thermally less stable than PCl5.
II: Size of As is more than that of P.
choose correct answer from the following
207
Main Group Elements
1. Statements I and II are true and II is the correct explanation of I.
2. Statements I and II are true but II is not the correct explanation of I.
3. Statement I is true and statement II is false.
4. Both the statements I and II are false.
77. Consider the following statements for Be2Cl4 (I), B2Cl4 (II) and Ga2Cl4 (III):
(A) There is an M-M (M= Be, B, Ga) bond in all.
(B) The oxidation state of Be, B and Ga is +2.
(C) The geometry around the central atom is planar for all.
(D) The geometry around the central atom is planar in I and II only.
The correct statement(s) is/are
1. A, B and C
2. A and B
3. D only
4. B. C and D
[CSIR DEC 2018]
78. The reaction of decaborane B10H14 , with acetylene in the presence of Et2S gives
(a) C2B10H12
(b) C2B8H10
(c) C2B10H14
(d) C2B9H11
79. In compound N3P3F6 , the geometry around nitrogen and phosphorus, respectively, are
(a) pyramidal and tetrahedral
(b) planar and tetrahedral
(c) pyramidal and planar
(d) planar and trigonal bipyramidal
80. The number of 2c-2e bonds ('x') of a molecule is related to 'N' (valence electrons) and ‘n’ (skeletal
atoms) by x=(8n-N)/2. For P4S3 , the values of x , N and n, respectively, are
(a) 7, 38 ,9
(b) 7 , 24 , 9
(c) 9, 38, 7
(d) 9, 24, 7
81. B2H6 reacts with

(A) water to give boric acid and H2
(B) oxygen to give B2O3 and H2
(C) water to give boric acid and H2O
(D) oxygen to give B2O3 and H2O
Correct statements from the above are
(a) A and B
(b) A and D
208
Main Group Elements
(c) B and C
(d) B and D
82. Match the items given in Column-I with those given in Column-II
Column-I Column-II
(A) Magic number (I) Nuclear fission
(B) Liquid drop model of nucleus (II) Q-value
(C) Actinides (III) Radioactivity
(D) Threshold energy (IV) Shell model of nucleus
(a) A-IV, B-1, C-III, D-II
(c) A-III, B-IV, C-I, D-II
(b) A-II, B-L, C-III, D-IV
(d) A-IV, B-III, C-I, D-II
[CSIR JUNE 2019]
83. The species that results by replacing one quarter of Si(IV) in pyrophyllite [Al2(OH)2 Si4O10] with
Al(III) [charge balance by K(1)] is
(a) muscovile
(b) phlogopite
(c) montmorillonite
(d) tale
84. The oxidation state of sulphur in the dithionous and dithionic acids, respectively, are
(a) +4, +6
(b)-4, +5
(c) +3, +5
(d) +3, +6
85. In the synthesis of polydimethylsiloxane , the chain forming, branching and terminating agents
respectively, are
(a) Me2SiCl2 , Me3SiCl and MeSiCl3
(b) Me2SiCl2, MeSiCl3 and Me3SiCl
(c) MeSiCl3 , Me2SiCl2 and Me3SiCl
(d) Me2SiCl2 , MeSiCl3 and Me4Si
86. The correct statements regarding Boron among the following

(1) Nuclear spin of 11B is greater than that of 10B
(II) The polarities of B-H bond and C-H bonds are opposite
(III) Cross-section of neutron absorption for 10B is much more than that of 11B
(IV) B reacts with boiling aq. NaOH solution to form NaB(OH)4
Are
(a) II and III
(b) I and II
209
Main Group Elements
(c) III and IV
(d) II and IV
87. Choose the correct statement(s) among the following

(I) LiF is more soluble than LiClO4 in water.
(II) The standard reduction potential [E0] of Li is more negative than that of Na
(III) The heat of hydration of Li+(g) is greater than that of Na+(g)
(a) I and II
(b) I and III
(c) II and III
(d) III Only
88. Choose the correct statement(s) among the following

(1) The dihedral angle in O2F2 is 00.
(II) OF2 is generally prepared by reacting fluorine gas with dilute (2%) aq. NaOH solution
(III) O2F2 can be readily reduced by H2S.
(a) I and II only
(b) I, II and III
(c) II and III only
(d) II only
[CSIR DEC 2019]
89. The common heptacity observed for coordination of C60 to a metal center is
(1) 2
(2)4
(3)5
(4)6
90. Match the items in Column I with those of Column II

Column I (species) Column I (structure/properties)
(a) NaH (i) Polymeric chain
(b) BeH2 (ii) Interstitial hydride
(c) HfH2.10 (iii) Tricapped trigonal prismatic
(d) [TcH9] (iv) Saline hydride
The correct match is.

(1)a-iv, b-ii c-iii, d-i
(2)a-i, b-iv, c-ii, d-iii
(3)a-iv, b-i, c-ii, d-iii
(4)a-iv, b-i, c-iii, d-ii
91. Consider the following statements:

210
Main Group Elements
(A) The highest oxidation state of Group 3 elements is more readily shown in their oxides than in
fluorides
(B)Fe can exist in-2 formal oxidation state also
(C) Mn , Tc and Re easily form M(II) compounds
(a) A and B
(b) A and C
(c) Band C
(d) C only
92.The correct statements for dithionite and dithionate anions from the following are
(A) both have S-S bond
(B) both are dianionic
(C) oxidation state of sulphur is +3 and +5, respectively
(D) sulphur in dithionate has lone pair of electrons
(1)A, B and C
(2)A, B and D
(3)B, C and D
(4)A and B only
[CSIR 2020]
93. Correct statement/s among the following with respect to ionization energy (IE) is/are
(i) (IE1 + IE2 + IE3) for indium is more than that of aluminium
(ii) IE1 of scandium is higher than that of cobalt
(iii) IE1 of gallium is lower than that of selenium
(iv) IE1 of nitrogen is greater than that of oxygen
(a) (ii) and (iv)
(b) (iii) and (iv)
(c) (i) and (iv)
(d) (ii) and (iii)
94. The reason for significantly high solubility of AgClO4 in benzene

than in alkane solvents is
(a) Alkane solvents are non- polar.
(b) Benzene is an aprotic solvent.
(c) PhAg is formed.
(d)Benzene acts as a soft base
95. Choose the correct statements for the Group 15 halides:

(i)AsCl3 can form complexes of type [AsCl4]- in the presence of a chloride source
(ii) PF3 acts as a strong a-donor ligand towards d-metals
(iii) In the solid state, SbF5 has a trigonal bipyramidal structure
(iv) The reaction of SbF5 with anhydrous HF generates [H2F]+ ions
211
Main Group Elements
a. (i) and (iv)
b. (ii) , (iii) and (iv)
c. (i) , (iii) and (iv)
d. (ii) and (iii)
96. The reaction of XeF6 with a limited amount of quartz gives compound A. Then on reaction with an
equivalent amount of XeO3. A gives B. The products A and B are, respectively
(a) XeOF2 and XeO2F2
(b) XeOF4 and XeO2F2
(c) XeOF2 and XeOF4
(d) XeO2F2 and XeOF4
97. The energies of interaction for (i) ion pair, (ii) ion-dipole, and (iii) dipole-dipole interactions are
inversely proportional to
(a) r, r2 and r3 respectively
(b) r2, r and r3 respectively
(c) r, r² and r6 respectively
(d) r2, r and r6 respectively
[CSIR JUNE 2021]
98. The correct order of the electron affinity for one-electron gain of the elements is
(a) F > Cl > Br
(b) P > N > As
(c) S > Se > O
(d) K > Li > Na
99. Which of the statements (A-D) given below are correct for B2H6 molecule:
A. Addition of 𝑬𝒕𝟐𝑶•𝑩𝑭𝟑 to NaBH4 in a polyether solvent produces B2H6.
B. It has 𝑫𝟐𝒅 symmetry.
C. Reaction of B2H6 with 𝑵𝑴𝒆𝟑 𝒈𝒊𝒗𝒆 𝑴𝒆𝟑𝑵•𝑩𝑯𝟑.
D. It is diamagnetic.
(a) A, B and C
(b) A, C and D
(c) A and B only
(d) B and D only
100. Which of the following reaction (s) do(es) NOT occur

212
Main Group Elements
(a) (i) and (iii)

(b) (i) and (ii)
(c) (i) only
(d) (iii) only

Stabilisation via back-bonding. Due to innert pair effect stability of +2 oxidation state increases
down the group.

Alkali metals in liq. NH3 ,act as source of electrons and are supposed to be a good one-electron reducing agents.
-
M+ (x+y )NH3→[M(NH3)x]+ +[ e (NH3)y].
These solvated electrons can reduce O2 molecule to superoxide ion.
- -
[e (NH3)y] +O2 → O2 + y NH3.
These superoxide ions can combine with solvated metal ion to give alkali metal superoxides.
+ -
[M(NH3)x] + O2 →MO2 + xNH3
Compounds Uses
(A) Na3PO4 Water softener
(B) Ar3PO4 Plasticizers
(C) Et3PO4 Insecticides

213
Main Group Elements
(D) CaHPO4.2H2O Toothpaste

4. Correct
answer: (a)
B2O3+ 3H2O → 2H3BO3 (orthoboric acid)
N2O5 + 3H2O → 2HNO3 (nitric acid)
SO3 + 3H2O → H2SO4 (sulfuric acid)
P4O10 + 6H2O → 2H3PO4 (orthophosphoric acid)
Correct answer is (a) closo-{BnHn} species has always -2 charge.

BCl→ pπ→-pπ back bonding
BCl> BPh3 > BMe3

(A) IE, for O and S are 1314 and 1000 kJ mol-1 difference 1314-1000=314
(B) For N and P IE, are 1402 and 1012 kJ mol-1 difference 1402-1012=390
(C) For P and As IE, are 1012 and 947 kJ mol-1 difference 1012-947 = 165 (less 300 kJ )
(D) Also for IE, difference is less than kJ mol-1

456 789
Na Na+(NH3)x + e-(NH3)y
NH4+ Br- + e-(NH3)y →NH3 + 1/2H2 +yNH3 + Br-
Na+(NH3)x + Br-→ NaBr + xNH3

(SN)x because it is a giant cross linked molecule and have mobile electrons.
Because P-O bond very strong affinity very high not easily break. So, R-O bond break.
214
Main Group Elements
The structure of Sodalite cage zeolites is a truncated octahedral (as shown below)
s =number of B-H-B bonds = 4

t = number of B-B-B = 0
y =number of B-B bonds = 1
x = number of BH2 groups + twice the BH3 groups = 2
Therefore, styx code = 4012

The Reaction mechanism of typical Bayer’s process is given below
Na2B4O7 +16Na +8H2 +7SiO2 → 4NaBH4 +7Na2SiO3
This is used for synthesis of NaBH4 from borax

The correct structure of beryllium nitrate contains Be cluster with 5 NO3 units and one O as a part of cluster. (as
shown below)
215
Main Group Elements

Smaller the internuclear distance between two atoms, stronger will be the bonds. The increasing inter nuclear
distance is as Cl-O < S-O < P-O< Si-O .Therefore strength of pπ-dπ bonding is Cl-O> S-O> P-O >Si-O.

NCl3 +4 H2O→NH4OH+ 3HOCl
PCl3+ 3H2O →, H3PO3 +3HCl (two different Acids) ,
AsCl3+3H2O → H3AsO3 + 3H2 (two different acids)

Alumino silicate is the most used catalyst in oil industry; mostly it is used for the process of Cracking.

Low oxidation state complexes are air sensitive as they easily lose electrons to oxygen, but they are not water
sensitive as they do not bind to a π–donor molecule like H2O.

PbCl2 and PbSO4 are ionic compounds and insoluble in cold water. Therefore, cannot be used for deposition of
Pb and Pb(Et) is toxic.

Among these elements K is least electronegative and F is most electronegative. Therefore electronegativity
difference is highest for the pair K, F.

C2B4H8
:;8
(BH)2B4H8 = B6H10 [ B6H6 ]-4 → nido borane
216
Main Group Elements

B(OH)3 +OH- ↔ [B(OH)4 ]- (reversible reaction)
In presence of ethylene glycol, B(OH)4- is consumed as shown below and boric acid behaves as strong acid.

Neso silicates (or Ortho or Island silicates) are the simplest silicates which contain discrete SiO44- tetrahedral
unit
Soro silicate (or Pyro silicate or disilicate) contain Si2O76- ions which are formed by joining two tetrahedral
SiO44- which share one oxygen atom at one corner (one oxygen is removed while joining).
Phyllo or two dimensional (2-D) silicates is (Si2O5)n2n- . Each SiO4 tetrahedron shares three oxygen atoms with
others and thus by forming two-dimensional sheets.
Tecto or three dimensional (3-D) or Framework silicates is (SiO2)n . All the oxygen atoms of SiO4 are shared
with other tetrahedra and thus by forming three-dimensional network.
217
Main Group Elements

As we go down the group in periodic table for sodium family, the number of electrons increases and their
attraction towards nucleus increases and simultaneously with addition of new energy shells but increase in
distance is more pronounced as that of increase in e- , So Na loses e-s very easily therefore lowest ionization
energy .
In the case of inert gas family, Ne has its complete octet, strongly connected with nucleus e attraction and do
not give e- s to lose easily therefore highest ionization energy.
Thus Na, Ne pair have highest difference in their first ionization energy in given option.

Nitrous acid (N₂O) which is commonly known as laughing gas used as a propellent in whipping cream. So, also
known as whippits or nangs.

The Flame proof fabrics contain urea and phosphoric acid H2NC(O)NH2.H3PO4

(A) N2O3 : HNO2 + HNO2 → N2O3 + H2O
(B) N2O4: HNO3 +HNO2 → N2O4 + H2O

As we move from Nb-Ta and Mo-W there is introduction of electron into f-orbital. As the shielding power of f-
orbital is very less. Therefore, as we move from La-Lu in 4f series the size decreases, this is termed as
Lanthanide contraction. This leads to slight increase in size of 5d metal than 4d. Due to this size of d and 5d
metals are nearly similar. Hence Nb-Ta and Mo-W have similar covalent radii.

218
Main Group Elements

FeCl3.6H₂O +SOCl2 → FeCl3 (s) + SO2(g) + HCl(g)

Large difference between the sizes of Li and Cs. So, it is difficult to get a solid solution of these two metals.

+ -
ClF3+SbF5 → [ClF2] [SbF6]
SbF5 is a very strong F- acceptor and leads to the formation of ionic compound.

Bond order=3 , bond order is directly propotional to bonding energy.
High bond order and HOMO LUMO gap

Cesium iodide (CsI) in crystalline form is used as the scintillator for the detection of protons and alpha particles.
Sodium iodide (NaI) containing a small amount of thallium is used as a scintillator for the detection of gamma
waves and zinc sulfide (ZnS) is widely used as a detector of alpha particles.
Since in the question, it is asked about radiations (that means gamma rays) thus answer should be NaI

H3PO3 is a dibasic and reducing in nature . Thus it should contain two OH groups in the structure.

In solid state, aluminum fluorides have 3D network structure unlike Al3Cl3

219
Main Group Elements
The diagram clearly indicates the four centered-two electron interaction (4c-2e). This takes place in Li4(CH3) 4
. The sp3 hybrid orbital is of carbon while the three s-orbitals are of three surrounding lithium atoms.

N3P3Cl3F (A) = only 1 isomer
N3P3Cl4F (B) = 3 isomer

N3P3Cl3F3(C) = 3 isomer
N3P3Cl2F4 (D) =3 isomer

220
Main Group Elements
N3P3ClF5 (E) = 1 isomer

Relative acidic strength of xenon fluorides follows order XeF6 > XeO3 > F > XeOF4 > XeF4, XeO2F2 > XeF2.
This order depends upon (i) number of lone pair (ii) number of ‘F’ atoms
C2B10H12 is show three isomeric derivative which is depend on the the temperature.

Styx rule B5 H 9
(BH)pHq (BH)5H4
S= number of BHB unit ↑ ↑
T= number of BBB unit p q
Y=number of BB unit
X= excess hydrogen attached to B alone.
Hydrogen balance
s+x=q s+x=4 s t y x
orbital balance 2 3 0 2
t+s=p t+s=5 3 2 1 1
Electron balance 4 1 2 0
p+q/2 = s+f+y+x t+y=5-4/2=3
p= f+ y + q/2
221
Main Group Elements
The reason is that HNO3 is better oxidising agent than H2SO4, also acts as dehydrating agent.

Chromium is extracted from chromite ore:
(I) 4FeCr2O4, +8Na2CO3 +7O2 → 8Na2CrO4 +2Fe2O2 +8CO2
(II) 2Na2CrO4+H2SO4 → Na2SO4 + Na2Cr2O7 + H2O
(III) Na2C2O7+2C → Cr2O7 +Na2CO3 +CO
(IV) Cr2O3 +2A1 → Al2O3 + 2Cr

The electronegativities of elements are
Ca Al As S
1.0 1.5 2.0 2.5

As positive charge increases the size decreases while with increase in negative charge increase the size. This is
due to increase in Zeff, in former case while decrease in Zeff, in later case. Hence, order of size is S2-> S > S2+ >
S4+

HF exist as H2F2 , and it act as fluoride donar if strong fluoride acceptor is present like SbF5, AsF5, Therefore,
the reaction will be HF 2 moles = H2F2
H2F2 (lewis base) + SbF5 (lewis base) → [H2F] ++ [SbF6] -
SbF5 act as Lewis acids as it has vacant 'd' orbital of suitable energy
222
Main Group Elements
All the ions are isoelectronic. Therefore, the size depends upon effective muclear charge.
=
Size of isoelectronic ions ∝
>
F- O2- Na+ Mg2+

Atomic number 9 8 11 12
Number of electrons 10 10 10 10
Hence, the order of size will be O2- > F- > Na+ >Mg2+
Since, atomic number increases.
Therefore, z, increases .
Therefore, size decreases.

The reaction is as follows
Ph2SiCl2 + 2H2O → Ph2Si(OH) 2 +2HCl
1:2 Diphenyl disilanol
Diphenyl- (A)
-dichloro silane
Now, (A) undergo condensation polymerisation to yield (B), which is an inorganic silicon, polymer, as follows

Diborane reacts with ammonia as
Here NH3 show unsymmetrical cleavage.

'Y' is actually [A+B].
In 'Y' 'B' part gives quintet and 'A' part gives triplet by 'B' and 'H' coupling.

The crown ether binds metal cation in their cavity. They are selective as they have fixed ring size.
223
Main Group Elements
Crown ether
Crown-4 Li+
crown-5 Na+
crown-6 K+
crown-7 Rb+
crown-8 Cs+
Therefore, 12-crown-4 is best suited for Li+ cation. After then as the size increases binding capacity decreases.

The reaction of XeF6 with NaNO3 takes place as
XeF6 + NaNO3 → XeOF4+ NaF+ NO2F

All the allotropic phosphorous forms changes into white P, discrete units. Which has structure.

Pseudo halogen are polyatomic analogous of Halogen whose chemistry resemble with true Halogen common
example. CN-, N-3 , SCN-, NCN2-.These anions contain nitrogen atoms.

;?9?; ==
The average of oxidation states is =
9 9
H5P3O10 = +5+3x-20 =0 , 3x =+15 , x=+5
H5P3O7 = +5+3x-14 = 0 ,x=+3
H5P3O8 = +5+ 3x-16=0 , x=+ 11/3
H5P3O9 = +5+3x-18=0 , x= +13/3

Due to IPE ns² electron-pair become inactive. In Pb
Therefore, the structure must be

224
Main Group Elements
Acidic strength of Borane depends upon
(i) number of Boron atoms
(ii) decapping
Hence, the correct order of acidity is B5H9 <B6H10 <B10H14

The structure of [Si6O18] -12, is
Hence, the number of linked tetrahedrals = 6

The size of ring = 12

ZSM-5 stands for Zeolite Socony Mobil-5, it is an alluminosillicate zeolite belonging to pentasil family of
zeolite. It’s chemical formula is NanAlnSi96-nO192.16H2O. It is widely used in industries for heterogeneous
catalyst for hydrocarbon isomeriasation.
The mechanism followed for the above reaction is
225
Main Group Elements

Structure of P4S3 is
Number of P-S bond=6

Number of P-P bond = 3

POCl3 → POCl2+ + Cl-
POCl6 + Cl →POCl4-
𝒍5𝒒 𝐏𝐎𝐂𝐥𝟑
(1) Et3N (OPCl2 .NEt3)+ + Cl-
POCl6 +Cl →POCl4- ( Cl- concentration is not enhanced)
-
𝒍5𝒒 𝐏𝐎𝐂𝐥𝟑
(ii) KCl K+ +Cl-
The Cl ion produced in this reaction increases the concentration of Cl- and it is not consumed by
-
POCl3
(iii) FeCl3 +OPCl3 →POCl2+ + CeCl4-
(iv) SbCl6 +OPCl3 → POCl2+ + SbCl6-

LaI2 exists as La+3 ( 2I- )(e-)
The electron present is responsible for metallic cluster and high electrical conductivity.

8C (graphite) + K+ (am)+e- (am) → [K (am)]+ [C8]- (s)
Due to the presence of unpaired electrons in π* band of graphite it is paramagnetic and its electrical
conductance increases. It has eclipsed layer structure

CCl4, or C6H6
6S2Cl2 +16NH3 S4N4 +S8 +12NH4Cl
Correct option (a)

67.
B4H10 + NMe3 → Me3NB3H7 + Me3NBH3
226
Main Group Elements

K + graphite →[graphite]- K+
H2SO4 +graphite = [graphite]+ HSO4-

Bi5+3 = 5x5-3 = 22
Hence, (4n+ 2), closo
On addition of 2 electron it become (4n+4), nido

NF has two isomers,

Generally, ionisation energy increases on moving from left to right in a period in periodic table.
• Ionisation energy decreases as we move down in given group
• Ionisation energy will be more for full filled and half filled orbital.

[PMo12O40]3- is less basic. It is slightly less basic than ClO4-

The structures of CsCl and CaB6 are as follows
CaB6 and CsCl both have BCC like structure, the B6 cluster is present at the body center of Ca lattice.

Zn → 3d10 4s2
227
Main Group Elements
2 1
Ga→ 4s 4p
Ge→ 4s2 4p2
As→ 4s2 4p3
Full filled and half filled orbital have higher ionization energy.
Hence, Ga have lowest first ionisation energy because removal of an electron Ga+ achieve stable nobel gas
configuration.

The above reaction undergoes as follows
=FF℃ H4IH45JK LMNOP4MQ5Q
XeF6 +2NF → Na2[XeF8] [XeF6] Perxenate + 2NaF
(Z) (A)

On descending the group, the stability of +3 oxidation state increases and that of +5 oxidation state decreases.
Size usually increases on descending the group (P = 1.10 A0 and As = 1.21 A0). Thus, AsCl5 is thermally less
stable than PCl5 and As is larger than P but less stability of AsCl5 , is not due to larger size of As, instead it is
due inert pair effect.

Structures of Be2Cl4 (I), B2Cl4 (II) and Ga2Cl4 are
Be2Cl4 = Planar
Be2Cl4 = Planar
GaI[GaIIICl4]
Ga2Cl4 = tetrahedral , No M-M bond

228
Main Group Elements
Valence electron (N) = P = 2s2 2p1 =5

S=2s2 2p4 = 6 4×5+6×3 = 38
R5SKQ
2c- 2e bond (x) = 9
Un - N Vx + N =U + 38
X= = n= = =7
V U U

The correct reaction of B2H6 with O2 and water are
O2 6H2O
B2O3+H2O B2 H 6 2B(OH)3 +H₂

Magic number →shell model of nucleus
Liquid drop model of nucleus → nuclear fission
Actinides →radioactivity
Threshold energy→ Q-value

[Al2(OH)2 Si4O10] KAl2(OH)2(Si3AlO10]
replaced by 1/4 of Si(IV)
by Al(III)and charge balance by K(I)
Pyrophyllite Muscovite

229
Main Group Elements

Poly dimethyl siloxane (PDMS) is :
In Siloxanes
Me3SiCl : used as terminating agents Me3SiCl + H2O →Me3Si(OH)+HCl

Me2SiCl2, used as chain forming Me2SiCl2+2H2O→ Me2Si(OH)2 + 2HCl
MeSiCl3: used as cross linkers for branching MeSiCl3+ 3H2O → MeSi(OH)3 + 3HCI

• Nuclear spin of 10B =3
Nuclear spin of 11B = 3/2
B→H C←H
Electronegitivity: 2.04 2.1 2.5 2.1
This indicates that polarities of B-H and C-H bonds are opposite
•Thermal neutron absorption cross section for 10B=3837 Barn and for 11B=0.005 Barn
•Boron resists attack by boiling conc. aqueous NaOH or fused NaOH upto 500°C.
B+ NaOH (aq) →No reaction
Boron react with fused alkali to give sodium metaborate and H2.

• LiF is sparingly soluble in water but for large anions such as ClO4- , the Li+ salts are soluble in water.
230
Main Group Elements
• Standard reduction potential [E0] of Li is more negative than that of Na.
Li+ (aq) + e- →Li (s) [E0]red = -3.04
Na+ (aq) +e- →Na(s) [E0]red = -2.71
•Enthalpy of hydration:
Li+ (g) [-520 kJ/mol] > Na+(g)[-406 kJ/mol]
The structure of O2F2 resembles that of H2O2, in its large dihedral angle, which approaches 90°. The reaction of
fluorine with a dil. aqueous solution of NaOH gives OF2 with sodium fluoride as a side-product.
2F2+ 2NaOH → OF2+ 2NaF + H2O
Oxidation (Reducing agent)

(+1) (0)
H2S + 4O2F2 → SF6 + 2HF + 4O2
Reduction (Oxidizing agent)

In fullerene the juncture bond (C=C) is the donor pi-bond. Hence, its common hapticity will be two

• Alkali metal hydrides are saline hydride.
• BeH2 has polymeric structure with 3c-2e bonding.
• Bigger metal hydrides are usually interstitial hydrides as H- can be trapped in their bigger voids.
• [TcH9]-2 is trigonal tricapped prismatic.

(A) The highest oxidation state +8 of group 8 elements is shown readily in oxides like OsO4 and RuO4 than in
fluorides like RuF8 and OsF8 because these fluorides are unstable due to increased steric hinderance.
(B) Fe can exist in-2 formal oxidation state also in carboxylate like [Fe(CO4)]-2.
(C) Mn forms Mn(II) compounds easily but Tc and Re rarely form M(II) compounds as indicentis their standard
reduction potentials.
231
Main Group Elements
+2 - 0
Mn (aq)+2e → Mn(s). E = -1.185 V
Negative value of E0 indicates that the reaction Mn to Mn+2 is feasible
Tc+2 (aq) +2e → Tc(s). E0 =+0.40V
Positive value of E0 indicates that the reaction Tc to Tc+2 is not feasible.

The structures of dithionite and dithionate are
Dithionite
S2O4-2
2x = 8-2
x = +3
Dithionate
S2O6-2
2x = 12-2
x = +5

•On moving down in a group, the atomic radius generally increases. Even though d-orbital is present in Indium,
its size is greater than that of aluminium as electron is added to 5s orbital which has much higher size than that
of 3s orbital of aluminium. Even after contraction, size of 5s orbital is greater than that of 3s orbital. Due to
higher atomic radius of In, its outer electrons experience lesser attraction towards nucleus hence, (IE1 + IE2 +
IE3) for In is less than that of Al.
•On moving along the period, size decreases thus, effective nclear charge increases and hence I.E. increases.
Therefore, IE1 of Co is higher than that of Sc and IE1 of Se is higher than that of Ga
• Nitrogen has stable half-filled 2s2 2p3 configuration thus, has higher IE1 than that of oxygen.

Alkane is a hard base react with hard acid. Benzene acts as a soft base reacts with soft acid (Ag+)

a.SbF5 + 2HF → [H2F]+ [SbF6]-
b.In the solid state, SbF5 is tetrameric thus, it has octahedral structure.
232
Main Group Elements
c.PF3 acts as a strong π-acceptor ligand towards d-metals.

d.AsCl3 may act as either a Cl- donor or acceptor with an appropriate reagent. Thus, in presence of a chloride
source, AsCl3 can form complexes of type [AsCl4]-

2XeF6 + SiO2 → 2XeOF4+ SiF4
quartz (A)
XeOF4+ XeO3 → XeO2F2
(A) (B)

The table below defines energies and their proportional interactins
Type of interaction Strength Energy-distance function
Covalent bond Very strong Complex, but comparatively long range
Ionic bond Very strong 1/r, comparatively long range
Ion-dipole Strong 1/r2, short range
Dipole-Dipole Moderately strong 1/r3, short range
Ion-induced dipole Weak 1/r4, very short range
Dipole-induced-dipole Very weak 1/r6, extremely short range
London dispersion force Very weak 1/r6, extremely short range

Generally for Nitrogen, oxygen and halogen family, electron gain enthalpy of 2nd period element is less than
that of 3rd period element.
In group 16, O,S,Se and Te. If we apply general trend, that electron gain enthalpy decreases down the group, so
the trend should follow O > S > Se > Te, but as mentioned elements of period 2 are generally have less electron
gain enthalpy, because of their smaller and more compact size, which leads to repulsion between incoming and
existing electrons. Thus oxygen has less electron gain enthalpy than others, so the order becomes S > Se > Te >
O.

Statement (A) is correct as,
𝐸𝑡V 𝑂 ∙ 𝐵𝐹9 + 𝑁𝑎𝐵𝐻; ⟶ 𝐵V 𝐻b + 𝐸𝑡V 𝑂
233
Main Group Elements
Point group of B2H6 is D2h, hence statement (B) is incorrect

Since, , thus statement (C) is correct
MOT of B2H6 is given by,
Hence, the molecule is Diamagnetic. Statement (D) is correct.

Reaction (i) and (ii) are possible but reaction (iii) cannot take place.

235
Nuclear Chemistry
[CSIR 2020]
1. Consider the nuclear reaction
234
92X + β +α → Y+ γ+ 2β+
Y is
(a) 92Y238
(b) 91Y238
(c) 93Y236
(d) 94Y238
[CSIR DEC 2019]

2. Identify from following the products of K-electron capture by the nucleus:
(A). neutron
(B). neutrino
(C). positron
Answer is
(1)A only
(2)A and B
(3)C only
(4)B and C
[CSIR JUNE 2019]

3. In neutron activation analysis the radiation commonly detected is
(a) α-rays
(b) β-rays
(c) γ-rays
(d) X-rays
4. The set among the following in which all numbers are magic numbers of nucleons is (a) 20, 28,
50 and 126
236
Nuclear Chemistry
(b) 24, 28, 82 and 126

(c) 20, 50, 80 and 184
(d) 28, 50, 82 and 180
[CSIR DEC 2017]

5. Among the following nuclear reactions of thermal neutrons, the cross section is highest for:
1. 92U235 + 0n1 → 92U235 + 0n1
2. 92U235 + 0n1 → 92U236
3. 92U235 + 0n1 → 90Th232 + 2He4
4. 92U235 + 0n1 → 36K94 + 56Ba140 + 20n1
[CSIR JUNE 2017]

6. Which one of the following pairs has two magic numbers for closed nuclear shells?
1. 8, 10
2. 10, 20
3. 50,82
4. 82, 130
7. Choose the correct statement for magnitude of threshold energy of an endoergic nuclear
reaction between stationary nucleus and a moving projectile.
1. It is greater than 'IQI' of nuclear reaction.
2. It has to be more than kinetic energy of a projectile.
3. It is less than 'IQI' of nuclear reaction.
4. It has to be equal to kinetic energy of a projectile.
8. Consider following statements for fission of U235 with thermal neutrons.

A. The % of nuclei undergoing unsymmetrical fission is maximum.
B. In each fission, one thermal neutron is produced.
C. Magnitude of energy released per fission is of the order 200 MeV
237
Nuclear Chemistry
Correct statement(s) is/are:

1. A and B
3. B and C
2. A and C
4. C only
[CSIR DEC 2015]

9. Spin motion of which of the following gives magnetic moment
A. Electron;
B. Proton;
C. Neutron
Correct answer is:
1. A and B
2. B and C
3.A and C
4. A, B and C
10. Identify radioactive capture from the following nuclear reactions:

1. 9Be (γ, n) 8Be
2. 23Na (n, γ) 24Na
3. 63Cu (p, p 3n 9α) 24Na
4. 107Ag (n, n) 107Ag
[CSIR JUNE 2014]

11. The nuclides among the following, capable of undergoing fission by thermal neutrons, are
(A) 233U
(B) 235U
238
Nuclear Chemistry
(C) 239Pu
(D) 232Th
(1) A, B and D
(2) A, C and D
(3) B, C and D
(4) A, B and C
12. For a low energy nuclear reaction, 24Mg (d, α) 22Na, the correct statements from the following
are
(1) Kinetic energy of d particle is not fully available for exciting 24Mg.
(2) Total number of protons and neutrons is conserved
(3) Q value of nuclear reaction is much higher in magnitude relative to heat of chemical reaction
(4) Threshold energy is ≤Q value.
13. The particles postulated to always accompany the positron emission among are:
(A) neutrino,
(B) anti-neutrino,
(C) electron,
(1) A, B and C
(2) A and B
(3) A and C
(4) B and C
CSIR JUNE 2013

14. For neutron activation analysis of an element, the favourable characteristics of both the target
and the product are from the following:
(A) high neutron cross-section area of target
(B) long half-life of the product
(C) low neutron cross-section area of target
239
Nuclear Chemistry
(D) low half-life time of the product.

The correct characteristics from the above are
(1) 1 and 2
(3) 2 and 3
(2) 3 and 4
(4) 1 and 4
[CSIR JUNE 2012]

15. In ‘carbon-dating’ application of radioisotopes, 14 C emits
(a) β-particle
(b) α-particle
(c) γ-radiation
(d) Positron.
[CSIR DEC 2011]
16. For the nuclear reactions.
(A) 𝟖𝟒Be → 2 𝟒𝟐He

𝟒𝟎
(B) 𝟖𝟎
𝟑𝟔Kr→2 𝟏𝟖Ar
𝟒𝟎
(Given masses: 8Be = 8.005300 , 4He=4.002603 and 𝟖𝟎
𝟑𝟔Kr =79.81638 , 𝟏𝟖Ar = 39.96238)
The correct statement is:

(a) (A) and (B) are both spontaneous fission processes.
(b) (A) is spontaneous fission but (B) is not.
(c) (B) is spontaneous fission but (A) is not
(d) Both (A) and (B) are not spontaneous fission processes.
CSIR JUNE 2011

17. The species 19Ne and 14C emit a positron and β-particle respectively. The resulting species
formed are respectively
240
Nuclear Chemistry
(a) 19Na and 14B

(b) 19F and 14
N
(c) 19Na and 14N
(d) 19F and 14B

With addition of α particle, atomic mass get increased by 4 and atomic number get increased by 2. With
addition of β particle, atomic number get decreased by value of 1 and with release of β+ particle atomic
number get decreased by 1.
Atomic mass of Y = 234+ 4 (due to addition of α) = 238
Atomic number of Y= 92-1 (due to addition of β-1) -2 (due to release of β+)
+2 (due to addition of α)
= 91
Thus, resulted nuclei is 91Y238

In electron capture process a proton captures an electron from k-shell, and convert into a neutron. In this
process an electron neutrino is also emitted. The reaction is as follows:
𝟏p
𝟏 + e- → 𝟏𝟎n + ῡe
Proton electron neutron neutrino

Henuce, the products are neutron and neutrino

In neutron activation analysis, the specimen is placed into a suitable irradiation facility and bombarded
with neutrons. This creates artificial radioisotopes of the elements present. Following irradiation, the
241
Nuclear Chemistry
artifical radioisotopes decay with emission of particles or, more importantly gamma rays, which are
characteristic of the elements from which they were emitted.

The magic numbers of nucleons 2, 8, 20, 28, 50, 82, 126.

The cross-section (σ) can be interpreted as the effective 'target area' that a nucleus interacts with an
incident neutron. Larger the effective area, greater the probability for reaction
In reaction 92U235 + 0n1 → 36K94 + 56Ba140 + 20n1 , one neutron react with 92U235 to give two neutron,
which have more tendency to react with other radioactive nuclei. Thus, increases effective area for
reaction.
2, 8, 20, 28, 50, 82 and 126 are magic number.

We have the relation between threshold energy and 'Q' of a reaction, as
Ma + MA
KTh = -Q
MA
Here, Ma = mass of moving projectile or bombarding particle

MA = mass of stationary nucleus
Also, for endoergic reaction, Q > 0
Therefore, magnitude of threshold energy.
Ma + MA Ma + MA
KTh = ⃒-Q⃒ ; >1
MA MA
⃒KTh⃒ > ⃒Q⃒

In fission of U235 with thermal neutrons
(1) On the average, each fission of a U235 nucleus produces about 2.5 free neutrons
(2) Each fission produce 200 MeV energy
242
Nuclear Chemistry
(3) Fission always occure in assymmetric fashion, it means number of nuclei undergoing unsymmetrical
fission is maximum.
Hence, correct statement is (1) and (3).

The reaction which involve evolution of γ radiation are called radioactive capture reaction
23
Na + .-n → 24Na + γ

The unstable nuclides like 233U, 235U and 239Pu, undergo fission by thermal neutrons. 232Th is a stable
nuclei, compared to others.
The kinetic energy of deuteron (d-particle) is very low, hence it cannot excite 24Mg nuclei.

Particles that are always to emit during positron emission
1
P1 → 0n1 + -.e + ῡ (antineutrino)

For an element the favourable characteristics both the target and the product in neutron activation is high
neutron cross-section area of the target and long half-life of the product.
In carbon dating , .0/C undergoes β- ray decay

.0 .0
/C → 1N +β

243
Nuclear Chemistry
(A) 𝟖𝟒Be → 2 𝟒𝟐He

Δm = 2x4.002603 - 8.005300 = -0.000094
There is mass loss. Thus, energy evolve.
Therefore, exothermic
𝟖𝟎 𝟒𝟎
𝟑𝟔Kr→2 𝟏𝟖Ar
Δm =2×39.96238 - 79.81638 = 0.10838

No mass loss, no energy realsed
Therefore, endothermic

6
-e45 (positron)
.3 .0
.-Ne 3F ;
6
-e95 (β- particles)
.0 .0
/C 1N ;

245
Inorganic Spectroscopy
CSIR JUNE 2011
1. In the EPR spectrum of tetragonal Cu(II) complex, when gǁ > g┴ > ge, the unpaired electron
resides in the orbital.
(a) dxy
(b) d x2-y2
(c) dz²
(d) dxz
2.Consider the compounds, (A) SnF4 (B) SnCl4 and (C) R3SnCl. The nuclaer quadrupole splitting
are observed for.
(a) (A), (B) and (C)
(b) (A) and (B) only
(c) (B) and (C) only
(d) (A) and (C) only
3. The correct value of isomer shift (in Mossbauer spectra) and its explanation for Fe(II)-TPP and
Fe(III)-TPP respectively from the following are:
(TPP= tetraphenylporphyrinate)
(A) 0.52 mms-1 (B) 0.45mms-1
(C) Increase in s electron density (D) Decrease in s electron density.
(a) (A) and (D); (B) and (C)
(b) (A) and (C); (B) and (C)
(c) (B) and (D); (A) and (D)
(d) (B) and (D); (A) and (C).
CSIR DEC 2011
19
4. In the F NMR spectrum of PF5 , the number of signals and multiplicity, at room temperature
are
(a) One, singlet
(b) One , doublet
246
(c) Two , doublet

(d) Two , singlet
5. In 57Fe Mossbauer experiment, source of 14.4 keV (equivalent to 3.48×1012 MHz) is moved
towards absorber at a velocity of 2.2 mms-1 .The shift in frequency of the source for this sample is:
(a) 35.5 MHz
(b) 25.5 MHz
(c) 20.2 MHz
(d) 15.5 MHz
CSIR JUNE 2012
6. If Mössbauer spectrum of Fe(CO)5 is recorded in the presence of a magnetic field, the original
spectrum with two lines changes into the one with
(a)Three lines
(b) Four lines
(c) Five lines
(d) Six lines
7. The metal complex that exhibits a triplet as well as doublet in its 31P NMR spectrum is
(a) mer-[IrCl3(PPh3)3]
(b) trans-[IrCI(Co)(PPh3)2]
(c) fac-[IrCl3(PPh3)3]
(d) [Ir(PPh3)4]+
8.The total numbers of fine and hyperfine EPR lines expected for octahedral high-spin Mn(II)
complexes are respectively (I= 5/2 for Mn)
(a) 3 and 30
247
(b) 5 and 33
(c) 5 and 30
(d) 4 and 24
9.The Mossbauer spectra of two iron complexes are shown below. They may arise from (i) high-
spin iron(III), (ii) high-spin iron(II) and (iii) low-spin iron(III)
CSIR DEC 2012
10. The number of lines exhibited by a high resolution EPR spectrum of the species,
[Cu(ethylenediamine)2]2+ is [Nuclear spin (I) of Cu= 3/2 and that of N = 1]
(a) 12
(b) 15
(c) 20
(d) 36
11.The recoil energy of a Mossabauer nuclide of mass 139 amu is 2.5 MeV. The energy emitted by
the nucleus in keV is:
(a) 12.5
(b) 15.0
(c) 20.5
(d) 25.0
12. Find out the number of lines in the 31P NMR signal for diagram
248
(a) 3
(b) 6
(c) 18
(d) 90
CSIR JUNE 2013

13. The number of EPR signals observed for octahedral Ni (II) complexes is
(a) One
(b) Two
(c) Three
(d) Zero
14. Among the following, those can act as Mössbauer muclei are
(A) 129I
(B) 57Co
(C) 57Fe
(D) 121 Sb
(a) A, B, C and D
(b) B, C and D only
(c) A, B, and D only
(d) A, C and D only.
249
15. For a tetragonally distorted Cr(III) complex, zero-field splitting results in the following
number of Kramers doublets:
(a) 1
(b) 2
(c) 3
(d) 4
16. In the presence of an external magnetic field (normal Zeeman effect), the transition 1D2 → 1P1
splits into
(a) 9 lines
(b) 8 lines
(c) 7 lines
(d) 6 lines
17. In Mössbauer experiment, a source emitting at 14.4 KeV (3.48x1018 Hz) had to be moved
towards absorber at 2.2 mms-1 for resonance. The shift in the frequency between the source and
the absorber is
(a) 15.0 MHz
(b) 20.0 MHz
(c) 25.5 MHz
(d) 30.0 MHz
CSIR JUNE 2014
18. The 19F NMR spectrum of CIF3 shows -

(a) doublet and triplet for a T-shaped structure
(b) singlet for a trigonal planar structure
(c) singlet for a trigonal pyramidal structure
(d) doublet and singlet for a T-shaped structure
250
19
19. The low temperature (-98°C) F NMR spectrum of SF4, shows doublet of triplets with the
point group symmetry.
(a) C 3v
(b) C4v
(c) Td
(d) C2v
20. The correct order of the isomeric shift in Mössbauer spectra ( 57Fe source) of iron compounds
is
(a) Fe(II) >Fe(III) > Fe(IV)
(b) Fe(III) > Fe(II) > Fe(IV)
(c) Fe(IV) > Fe(III) Fe(II)
(d) Fe(IV) >Fe(II) > Fe(III)
21. The number of lines in the ESR spectrum of CD3 is (the spin of D is 1)
(a) 1
(b) 3
(c) 4
(d) 7
CSIR DEC 2014

22. EPR spectrum of a free radical containing nuclei with nonzero nuclear spin is obtained if the
following selection rules are observed-
(A) Δms = 0 , Δml = 0
(B) Δms = ±1, Δml = 0
(C) Δms = ±1, Δml = ± 1
(D) Δms = 0, Δml = ± 1
CSIR JUNE 2015

251
23. The 119Sn NMR chemical shift (approximately in ppm) corresponding to (ղ 5-Cp)2 Sn (relative
to Me4Sn) is
(a)-4
(b)+137
(c)+346
(d)-2200
24. The reduced form of a metal ion M in a complex is NMR active. On oxidation, the complex
gives an EPR signal with gǁ = 2.2 and g╧ = 2.0. Mossbauer spectroscopy cannot characteristic the
metal complex. The M is
(a) Zn
(b) Sn
(c) Cu
(d) Fe
25 Mössbauer spectrum of a metal complex gives information about

(A) oxidation state and spin state of metal
(B) types of ligands coordinated to metal
(C) nuclear spin state of metal
(D) geometrey of metal
Correct answer is
(a) A and C
(b) B and C
(c) A, B and D
(d) B and D
CSIR JUNE 2016

252
26. Identify correct statements for the EPR spectrum of VO(acac)2 [with square pyramidal
geometry at vanadium] at 77K [ I (51V) = 7/2]
(A) It has two g values
(C) It has one g value
(B) It has 8 lines only
(D) It has two patterns of 8 lines each.
Correct statements are -
(a) A and D
(b) A and C
(c) B and C
(d) B and D
27. The numbers of lines shown by the BH3 part of the molecule Ph3P.11BH3 in the 1H and 11B
NMR spectra are, respectively [I (11B) = 3/2 ; I(31P) = 1/2]
(a) 8 and 8
(b) 4 and 8
(c) 3 and 6
(d) 6 and 3
28. To record Mössbauer spectrum of Fe containing samples, a source 'X' is used. X after a
nuclear transformation (Y), gives γ -radiation used in Mössbauer spectroscopy.
(a) 57Fe , β-emission
(c) 57Co, electron capture
(b) 57Co, β-emission
(d) 57Fe, electron capture
CSIR DEC 2016

19
29. The expected number of F NMR spectral lines, including satellites, for [XeF5]- is [Abundance
of 129Xe (I=1/2) = 26%]
(a) two
253
(b) twenty one

(c) three
(d) one
30. The reaction between PI3, PSCl3 and zinc powder gives P3I5 as one of the products. The
solution state 31P NMR spectrum of P3I5 shows a doublet (δ 98) and a triplet (δ 102). The correct
structure of P3I5 is
(a)
(b)
(c)
(d)
31. For complex A, deuteration of NH protons does not alter the EPR spectrum. The number of
hyper fine lines expected in the EPR [I( 63Cu)=3/2] spectrum of A is
(a) 20
254
(b) 12
(c) 60
(d) 36
32. Number of lines in the 19F NMR spectrum of F2C(Br)-C(Br)Cl2, at -120°C assuming it a
mixture of static conformations given below, are
(a) one
(b) two
(c) four
(d) five
CSIR JUNE 2017

33. Mössbauer spectrum of complex [Fe(1, 10-phenanthroline)2(NCS)2] shows two lines at 300 K,
four lines at 186 K, and again two lines at 77 K. This can be attributed to
A. change in the coordination mode of NCS
B. change in the spin-state of iron
C. cis-trans isomerisation
D. change in metal-ligand bond distances
(a) A and B
(b) B and C
(c) A and C
(d) B and D
255
34. (R3Ge)2 on photolysis gives a radical which shows ESR spectrum. The ESR signals carrying
the signature of 73Ge (I= 9/2) are in terms of
(a) Nine lines
(b) Ten lines
(c) Two lines
(d) One line
35. The 31P(1H) NMR spectrum of 2,2,6,6-N4P4Cl4(NMe2)4 is expected to show

(a) two triplets
(b) two doublets
(c) one doublet and one triplet
(d) one quartet and one doublet
CSIR DEC 2017

36. Assuming 1JPH > JPB the expected 31P NMR spectrum of H3P. 11BCl3 [for 11B, I = 3/2] is
(a)
(b)
(c)
256
(d)
37. The number of lines in EPR spectrum of CD3 (ID = 1) is

1. 3
2. 5
3. 7
4. 9
CSIR DEC 18
38. In the 31P{1H} NMR spectrum of a diamagnetic complex mer-[M(PR3)3Cl3] (M=transition
metal , I=0) expected number of resonance(s) is
(a) Three
(b) One
(c) Two
(d) Six
39. The 31P{1H} NMR spectrum of cis-[Pt(PEt3)2Cl2] (195Pt (33.8% abundance) I = 1/2; its other
isotopes are (NMR inactive: 31P : I= 1/2) is comprised with satellite peaks of a
(a) triplet
(b) singlet
(c) doublet
(d) quartet
40. Consider the following statements for [FeO4]-2

(A) It is stable in the pH range 0-14
257
(B) It is stable in strongly basic medium only

(C) It is a very strong oxidizing agent
(D) The isomer shift in its Mossbauer spectrum is more negative compared to that of FeCl3 .
(a) A, C and D
(b) B, C and D
(c) B and C
(d) C and D
CSIR DEC 2019

41. For an a an octahedral Cu+2 complex depicting axial EPR spectrum (g), the geometry of Cu
and the orbital containing the unpaired electron are respectively
(a)Tetragonally elongated, d x2-y2
(b)Tetragonally compressed, dz²
(c)Tetragonally elongated, dz²
(d)Tetragonally compressed, d x2-y2
42. For the complex shown below in non-fluxional state, the expected 31P{1H} NMR resonance(s)
is/are [31P= I=1/2]
(a)one singlet
(b)one doublet
(c)two Singlets
(d)two doublets
43. In Mossbauer spectrum of a sample containing iron recorded in the presence of a static
magnetic field, the number of possible allowed transition(s) is
258
(a)Two
(b)Four
(c)Six
(d)Eight
CSIR JUNE 2021
44. Consider the following statements regarding EPR spectra.

(A) For allowed transitions, ∆𝑴𝑺 = ±𝟏 𝒂𝒏𝒅 ∆𝑴𝒍 = 𝟎
(B) For allowed transitions, ∆𝑴𝑺 = 𝟎 𝒂𝒏𝒅 ∆𝑴𝒍 = ±𝟏
(C) Tetragonally elongated Cu(ll) complexes have, 𝒈∥ > 𝒈0 .
(D) The orbital considered as ground state for tetragonally compressed Cu(II) complexes is dx2-y2 .
(a) (A), (C) and (D)
(b) (B), (C) and (D)
(c) (A) and (C) only
(d) (B) and (D) only
259
CORRECT OPTION & EXPLANATION%
1. Correct answer: (b).

Gives the evidence that Cu on is present in tetragonally distorted octahedral field, the unpaired electron
resides in the orbital d x2-y2

SnF4 is ionic, here Sn+4 = 5s0 so no quadrupole splitting.
SnCl4 is covalent, and Sn is sp3 hybridised, So there is s-electron density in the molecule.
Hence quadrupole splitting is possible.
R3SnCl is covalent, and Sn is sp3 so there is s-electron density in the molecule.
Hence quadrupole splitting is possible.

Both Fe(II) TPP and Fe(III)-TPP are square planar (because of tetradentate-planar, porphyrine type
ligand), and both Fe(II) and Fe(III) are dsp2-hybridised, so there is s-electron density, which is
responsible for their quadrupole moment and existence of mossbauer spectra.
So both Fe(II)-TPP and Fe(III)-TPP show increase in s-electron density, but Fe(II) has higher s-electron
density. So Fe(II) has isomer higher shift (0.52 mms-1) than Fe(III) (0.45 mms-1).

260
At room temperature due to rapid interconversion of axial and equatorial F atoms, all the F will be
19
equivalent. Hence F NMR of PF5 at room temperature will appear as doublet of 5F.

𝑉 𝑣
Frequency shift (∆v) =
𝑐
Where V =relative velocity of source and observer
𝑣 =frequency of emitted radiation

𝟏𝟎8𝟑 𝒎
𝟐. 𝟐× ×𝟑. 𝟒𝟖×𝟏𝟎𝟏𝟖 𝑯𝒛
∆𝒗 = 𝒔 = 𝟐. 𝟓𝟓×𝟏𝟎𝟕 𝑯𝒛 = 𝟐𝟓. 𝟓𝑴𝑯𝒛
𝟑×𝟏𝟎𝟖 𝒎/𝒔
Triplet as well as doublet indicate 3 phosphorus atoms in the molecules in two sets
2P = doublet , 1P= triplet
That is possible in mer-[IrCl3(PPh3)3]
fac-[IrCl3(PPh3)3] will give singlet of 3P
261
trans-[IrCI(Co)(PPh3)2] will give singlet of 2P.

[Ir(PPh3)4]+ will give singlet of 4P.

The total numbers of fine and hyperfine EPR lines expected for octahedral high-spin Mn(II), I=5/2
Numbers of fine = No. of unpaired electron in Mn=5
Numbers of hyperfine EPR lines = No. of unpaired electron x (2nI+1)
n= no. of Mn atom = 1 , I= nuclear spin of Mn = 5/2
E
Numbers of hyperfine EPR lines = 5 × 2×1× + 1 = 5×6 = 30
F

(1)Fe3→High Spin-d5 →Spherical electronic configuration
E
𝑇FM 𝐸MF → No quadrupole splitting, singlet signal as shown in (B)
(2)Fe2 →High-Spin- d6→axial electronic configuration

O
𝑇FM 𝐸MF →quadrupole splitting, gives doublet signal as shown in (A)
(iii) Fe3 → Low-Spin- 𝑇FM

E
𝐸MP → Axial electronic configuration quadrupole splitting,doublet signal as
shown in (A)
Q R
mICH = ± , mlN =1; mlCu = ,
F F
Multiplicity =(2nnIN+1 )( 2nnICu+1 +1)= (2x4x1+1) (2×1×3/2+1)=9x4=36

262
ST
Recoil energy =R =
FUV T
ERW XT
= 𝑒𝑉
FUV T
ERW XT
= 2.5×10W =
QRZ×ZRQ.E
F.E×QRZ×ZRQ.E×QP[
E= = 24.57×10R eV= 25 keV
ERW
Four H1 are equivalent. Two nitrogen are equivalent.

Two fluorine are equivalent. One 2H is separate.
Q Q Q Q
Multiplicity= 2×4× + 1 2×2× + 1 2×2× + 1 2×1× + 1 = 5×3×3×2 = 90
F F F F
4H1 2N15 2F 1H

If the system has an even number of unpaired electrons then zero field splitting within the ground state
may result in the EPR transitions being undetectable and only one EPR signal is observe . Since Ni(II)
octahedral complex has two unpaired electrons, therefore, number EPR signals is one.

129
I, 57Fe , 121 Sb Mössbauer nuclei and they fulfuil all the properties for that 57Co is unstable nuclei
which is used as y-source in the Mössbauer spectro photometer for 57Fe study.

For systems with more than one unpaired electrons s >1/2 the ground state can be split in the absence of
external magnetic field due to local site symmetry-the zero field splitting. For odd electrons systems,
263
this results in pairs of energy levels known as Kramer's doublets. Since Cr(III) has three unpaired
electrons, therefore number of Kramer's doublets in tetragonally distorted Cr(III) complex in zero field
splitting is 2.

SELECTION RULE
ΔML= 0, ±1 ( for Zeeman effect)

ijkkl mn imopVk ×npkqokrVs F.F×QPxy z/i×R.O{×QP|} ~•
𝐷𝑜𝑝𝑝𝑙𝑒𝑟 𝑠ℎ𝑖𝑓𝑡 = =
ijkkl mn tuMvw R×QP} z/i
=2.552x10€ = 25.5 MHz
There are two types of F Fa , Fb

19
F = F b = doublet due to F a
19
F = F a = triplet due to F b
264
T shaped structure.

19
The low temperature , (-98°C) F NMR spectrum of SF4 - doublet of triplet
Q
Equatorial F= 2x 2 x + 1 = 3 , n=2 (axial F)
F
Q
Axial F= 2x 2 x + 1 = 3 , n=2 (Equatorial F)
F
One C2 axis is present (passes through S and bisect the line joining the two F atoms each) ϭh is absent .
2ϭv present (molecular plane and the plane bisecting the line joining the two Fatoms passing through S).
Symmetry elements E , C2 ,2ϭv
Point group symmetry = C2v

Fe(II)= 3d6 4s0 , Fe(III)=3d5 4s0 , Fe(IV)= 3d4 4s0
Isomer shift in Mössbauer spectra depend on the s-electron density and d-electron density increase the s-
electron density decrease the isomer shift increase the d-electron density increase the isomer shift.
So, so correct order, Fe (II) > Fe (III) >Fe (IV).

CD3 (ID= 1)
(2nI+1)= (2x3 x 1 + 1) = 7

Selection rule for EPR , Δms = ±1, Δml = 0.

265

Oxidation of Zn to Zn will be diamagnetic hence EPR inactive.
Fe and S - Inactive.
EPR spectroscopy generally used for the species have one or more unpaired electron.
Cu(II) are EPR active because non-paired electron.

Mössbauer spectrum of a complex gives information about
(1) Oxidation state and spin state of metal
(2) Types of ligands co-ordinate to metal define by quardurpole splitting on the behalf of electronic
environment of ligand symmetry.
(3) Also information about geometry of metal
For vanadium, I= 7/2 . So, 2nI+1= 2(1)(7/2) + 1 = 8

So, in EPR spectrum it has two g values and it has two patterns of 8 lines each.

BH3 part of the molecule Ph3P.11BH3
1
H NMR spectrum (2N1I+1) × (2N2I+1) = (2x1x3/2+1)x (2x1x1/2+ 1) = 4x2=8
11
B spectrum (2N1I + 1) × (2N2I+1) = (2x3x1/2+ 1)×(2x1x1/2+ 1) = 4x2 = 8

266
57 57
Fe* can be prepared by electron capture process from radioactive F€CO.

{•E•Q
[XeF5]- = = 7 = sp3d3 hybridzation
E
Shape = Pentagonal Planar
as 74% Xe are NMR inactive hence a singlet of five fluorine and due to 26% nuclei a doublet of
satellite.
Hence, total number of signal is 3.

267
One C2 axis and one plane of symmetry exist in this molecules,

So, two types of phoshphorous atoms
For aP (2NI+1)= [2x1x1/2+1] = 2 (doublet)
For bP (2NI+1) = (2x2x1/2+1) = 3 (triplet)

Number of hyperfine line (due to Cu and nitrogen)
(2NICu +1) (2NIN+1)
(2x1x3/2+1) (2×2×1+1)
4x5=20.
Both fluorine in same environment.

So, form doublet (2NIF+1)=(2×1×1/2+1) =2
Both are mirror image to each other

but fluorine in different enviornment
(2x2x1/2+1) = 3 triplet
So, total number of line 2+3=5

268
• Since NCS is ambidentate ligand therefore change in co-ordinate mode

• Change in the spin-state of iron at high temperature

(R3Ge)2 → 2R3Ge (radical) in R3Ge (radical)
Multiplicity = (2nI + 1) = 2x1x9/2+ 1 = 10 lines
73
Ge [I = 9/2]
31
P {1H} → (2NI+1)=[2×2×1/2+1]=3 (triplet)
31
P {1H} → (2NI+1) = (2x2x1/2+1)=3 (triplet)

H3P. 11BCl3
31
P NMR→(2NIH+1) for 3H=(2x3x1/2+1)=4(quartet)→1:3:3:1
P NMR → (2NIB+1) for B = (2x3/2x1+1)=4(quartet)→1:1:1:1
Intensity ratio: 1:1:1:1:3:3:3:3:313:3:3:1:1:1:1
269

In CD3 molecule => I = 1
Number of EPR lines= (2NI+1) = (2x3x1+1) =7
mer-[M(PR3)3Cl3]

Out of 100% molecule of cis-[Pt(PEt3)2Cl2] , 33.8% [Pt195(PEt3)2Cl2] having doubled satellite in 31P
NMR due to 1JP-Pt coupling and 66.2% [Pt (PEt3)2Cl2] having Singlet signals in 31P NMR due to 1JP-Pt
coupling absent.
Overall the 31P NMR signal will be singlet signal with 33.8% doublet satellite as given below.
OR
The 31P {1H} NMR spectrum is comprised with satellite peak of a singlet signal.

[FeO4]-2
270
• It is stable in strongly basic medium

• Powerful oxidizing agent
• The isomer shift of its Mossbauer spectrum is more negative compared to that of FeCl3
gǁ > g ╧ >g2
the evidence that Cu on is present in tetragonally distorted octahedral field,
Ground state tetragonally elongation & unpaired electrons in d x2-y2
Both phosphorus are chemically different 2JP-P and 3JP-P and are possible,
Signal for =(2NI* +1)=[2x1×1/2+1]=2→ doublet
Signal for P* = (2NI +1)=(2x1x1/2+1)=2→doublet

271

Selection rule for allowed transition is ∆𝑀ƒ = ±1 𝑎𝑛𝑑 ∆𝑀t = 0 , thus statement (A) is correct
In tetragonally elongated Cu(II) complex, more electron density is along dz2 orbital hence 𝑔∥ > 𝑔0
Ground state for tetragonally compressed Cu(II) complexes is dx2-y2 .

273
Lanthanides & Actinides
CSIR JUNE 2011

1. Among the following statements, identify the correct ones for complexes of lanthanide (III) ion.
(A) Metal-ligand bond is significantly ionic.
(B) Complexes rarely show isomerism.
(C) The coordination number is not more than 8.
(D) The magnetic moments are not accounted even approximately by spin only value for majority
of lanthanides.
(a) A, B and D only
(b) A, B and C only
(c) B and C only
(d) A and D only
2. Statement I: The sizes of Zr and Hf are similar

Statement II: Size of Hf is affected by lanthanide contraction.
(a) Statement I and II are correct and II is correct explanation of 1.
(b) Statement I and II are correct but II is not a correct explanation of 1.
(c) Statement 1 is correct and II is incorrect
(d) Statements I and II both are incorrect.
3. The electronic configuration for gadalonium (Gd) is [Xe]4f7 5d16s², where as that of Gd²+is:
(a) [Xe]4f55d6s2
(b) [Xe] 4f6 6s2
(c) [Xe]f6 5d1 6s1
(d) [Xe]4f7 5d1
4.Uranium fluorides co-precipitate with

(a) CaF₂
(b) AgF
(c) LiF
274
(d) MgF₂
[CSIR DEC 2011]
5.The actual magnetic moment shows a large deviation from the spin-only formula in the case of
(a) Ti¹+
(b) V3+
(c) Gd3+
(d)Sm3+
[CSIR JUNE 2012]

6. The least basic among the following is:
(a) Al(OH)3
(b) La(OH)3
(c) Ce(OH)3
(d) Lu(OH)3
7. The pair of lanthanides with the highest third-ionization energy is:

(a) Eu, Gd
(b) Eu, Yb
(c) Dy, Yb
(d) Lu, Yb
8.The lanthanide(III) ion having the highest partition coefficient between tri-n-butylphosphate
and concentrated HNO3 is:
(a) La(III)
(b) Eu(III)
(c) Nd(III)
(d) Lu(III)
[CSIR DEC 2012]

275
9. Which one of the following shows the highest solubility in hot concentrated aqueous NaOH?
(a) La(OH)3
(b) Nd(OH)3
(c) Sm(OH)3
(d) Lu(OH)3.
10. Consider the ions Eu(III), Gd(III), Sm(II) and Lu(III). The observed and calculated magnetic
moment values are closest for the pair
(a) Gd(III), Lu(III)
(b) Eu(III), Lu(III)
(c) Sm(III), Gd(III)
(d) Sm(III), Eu(III)
[CSIR June 2013]

11. Consider following lanthanide (III) ions
(A) Nd(III)
(B) Gd(III)
(C) Dy(III)
The magnetic moment closest to the spin only value is(are) for
(a) B only
(b) A and B only
(c) A and C only
(d) B and C only
12. The ground state term symbol for Nb(atomic number 41) is 6D. The electronic configuration
corresponding to this term symbol is
(a) [Kr]4d3 5s2
(b) [Kr]4d4 5s1
(c) [Kr]4d5 5s0
276
(d) [Kr]4d3 5s1 5p1
[CSIR DEC 2013]

13. The ground state forms of Sm and Eu respectively, are
(a) 7F0 and 6H5/2
(b) 6H5/2 and 7F0
(c) 2F5/2 and 5I4
(d) 7F6 and 2F7/2
[CSIR JUNE 2014]

14. A comparison of the valence electron configuration of the elements, Sm and Eu suggests that
(a) Sm is a better one electron reductant than Eu
(b) Sm is a better one electron oxidant than Eu
(c) Facile oxidation state is +2 for both the elements
(d) both of these display similar redox behavior
[CSIR DEC 2014]

15.The correct order of the retention of cations on a sulfonated cation exchange resin column is
(a) Ag+ > K+ > Na+ > Li+
(b) K+ > Na+ > Ag+ > Li+
(c) Li+ > Na+ > K+ > Ag+
(d) Li+ > Na+ > Ag+ > K+
16. Hindered ß-diketonates like dpmH (dpmH = dipivaloylmethane) are used for the separation of
lanthanides because complexes formed with dpmH can be separated by
(A) Gel permeation chromatography
(B) Gas chromatography
(C) Gel filtration chromatography
(D) Ion exchange chromatography
277
[CSIR JUNE 2015]

17. Consider the following statements with respect to uranium
(A) UO2+ disproportionates more easily than UO2+2
(B) U3O8 is its most stable oxide of U
(C) Coordination number of U in [UO2(NO3) 2(H₂O)2].4H,O is six.
(D) UO2+2 is linear
The correct set of statements is
(a) A, B and D
(b) A, C and D
(c) B, C and D
(d) A, B and C
18. Consider the following statements for (NH4) 2[Ce(NO3) 6](Z)

(A) Coordination number of Ce is 12
(B) Z is paramagnetic
(C) Z is an oxidising agent
(D) Reaction of Ph3PO with Z gives a complex having coordination number 10 for Ce.
(a) A, B and C
(b) B, A and D
(c) B, C and D
(d) A, C and D
[CSIR DEC 2015]

19.The metallic radii are abnormally high for which of the following pairs?
(a) Eu, Yb
278
(b) Sm, Tm
(c) Gd, Lu
(d) Nd, Ho
20. Which of the following statements are TRUE for the lanthanides?
(A) the observed magnetic moment of Eu at room temperature is higher than that calculated from
spin-orbit coupling
(B) Lanthanide oxides are predominantly acidic in nature
(C) The stability of Sm(II) is due to its half-filled sub-shell.
(D) Lanthanide (III) ions can be separated by ion exchange chromatography
Correct answer is
(a) A and D
(b) A and B
(c) A and C
(d) B and C
[CSIR JUNE 2016]

21. For monoionic complex [UO2(NO3)3 ]-1 the correct coordination number and geometry
respectively, are
(a) 8 and hexagonal bipyramidal
(b) 5 and square pyramidal
(c) 8 and square antiprism
(d) 5 and trigonal bipyramidal
22. The g values for Ce+3 (4f1) and Pr+3 (4f2) are, respectively
(a) 3/7 and 2/5
(b) 5/7 and 4/5
(c) 6/7 and 3/5
279
(d) 6/7 and 4/5
[CSIR JUNE 2017]

23. Which one of the following pairs has two magic numbers for closed nuclear shells ?
(a) 8, 10
(b) 10, 20
(c) 50, 82
(d) 82, 130
24. The calculated and observed magnetic moments (in B.M.) of aqua complex of a lanthanide ion
are 0 and ~3.5, respectively. The lanthanide ion is
(a) Pm+3
(b) Pr+3
(c) Eu+3
(d) Sm+3
[CSIR DEC 2017]

25. Match lanthanides in Column I with their properties in Column II
Column I Column II
A. Lu (i) Reagent in oxidation state IV
B. Eu (ii) Ml, of metallic lustre
C. Ce (iii) Diamagentic M(III)
D. Tb (iv) Pink in oxidation state III
Correct match is
(a) A-(iii), B-(ii); C-(i); D-(iv)
(c) A-(iv), B-(ii); C-(i); D-(iii)
(b) A-(ii), B-(iii); C-(iv); D-(i)
(d) A-(iii), B-(ii): C-(iv); D-(i)
280
26. Consider the following statement(s) for actinides (An):

A. Oxidation states greater than +3 are more frequent in An compared to lathanides (Ln)
B. Some An(III) ions show d-d transitions
C. UO2+2 and PuO2+2 are stable
D. Some of actinides do not have radioactive isotopes
(a) A and C
(b) Band D
(c) A, B and C
(d) B, C and D
[CSIR JUNE 2018]

27. Trivalent lanthanide ion having isotropic magnetic susceptibility is
1. Eu+3
2. Gd+3
3. Yb+3
4. Lu+3
28. Match fluorescence colours given in column A with lanthanide ions given in Column B
Correct match is
1. (i)-(a); (ii) - (c); (iii)-(b); (iv) - (d)
2. (i)-(d); (ii)-(c); (iii)-(b); (iv) - (a)
3. (i)-(a); (ii)-(b); (iii) - (c); (iv)-(d)
4. (i)-(c); (ii)-(b); (iii)- (d); (iv)-(a)
281
[CSIR DEC 2018]

29. Consider following statements for Eu+3
(A) The positions of sharp bands in UV-vis spectra of its complexes depend heavily on the ligand
environment
(B) Its ground state term symbol is 7F0
(C) The observed magnetic moment is due to populated higher level
(D) At 2K its magnetic moment approaches to zero
The set of correct statements is
(a) A, C and D
(b) B, C and D
(c) A, B and D
(d) A, B and C
[CSIR JUNE 2019]

30. The coordination number of Gd in GdCl3.6H2O is
(a) 3
(b) 6
(c) 8
(d) 9
[CSIR DEC 2019]

31. Pair of lanthanide ions which show significant deviation between the experimental and
calculated magnetic moments, considering contribution from the ground state only
(1)Gd and Lu
(2)Sm and Th
(3)Eu and Tb
(4)Sm and Eu
282
[CSIR 2020]
32. The pair in which both actinides show +3 oxidation state only is
(a)Ac and Lr
(b)Ac and No
(c)Cm and Bk
(d)Cm and Lr
33. The correct match for column A with column B is:
1. (a) - (iv) , (b) - (i) , (c)-(ii), (d) - (iii)

2. (a) - (ii), (b) - (iv) , (c) - (iii), (d) - (i)
3. (a) - (ii) , (b)-(iv) , (c)-(i) , (d)-(iii)
4. (a)- (i) , (b)- (iii) , (c)-(ii) , (d) - (iv)
[CSIR JUNE 2021]
34. The effective magnetic moment (in BM) for a lanthanide f10 ion is approximately
(a) 10.6
(b) 9.92
(c) 9.59
(d) 7.94
283
*** CORRECT ANSWERS & EXPLANATIONS ***

(A) Correct, As 4f-electrons are too well shielded to interact, so they are like inert gas-type ion, like
those of alkaline earth metals, that attracts ligands only by overall electrostatic forces.
(B) Correct, Lanthanides owing to the unavailability of orbitals for bonding, high basicity and rather
large size of Ln3+, form few complexes and mostly with oxygen or oxygen plus nitrogen chelating
ligands such as -dietones, hydroxy acids EDTA etc. So, they rarely show isomerism and also lability of
ligands make the isolation of isomers difficult.
(C) Incorrect, C.N. more than 8 are common, due to their larger size and smaller chelating ligand like,
NO3- SO2-4etc.eg. [Ce(NO3)6]2-,C.N=12
(D) Correct, As 4f electrons are well shilded from external fields by the overlying 5s and 5p elec trons.
Thus the magnetic effect of orbital motion is cannot be neglected.

As we move from 2d row transition element (Zr) to 3 row transition element (Hf), size should increase,
but due to lanthanide contraction offset the increase, so Zr and Hf have almost similar size.
3. Correct answer : (d)
64Gd = [Xe]4f7 5d16s2, Gd+2=[Xe]4f7 5d1 6s°

Removal of electrons takes place from the outermost orbital only.
4. Correct answer : (a)

Uranium fluorides co-precipitate with CaF2
Sm3+due to spin-orbital coupling

Al(OH)3 Amphoteric whereas hydroxides of lanthanoids are all base.
284

Eu+2 →4f7 →Half-filled→ stable
Yb²+→4f14→ Completely filled → stable

Smaller the size of Lu3+ ion, higher will be the partition coefficient.

Since size of Lu is smallest, therefore Lu(OH)3 complex most easily formed with NaOH and dissolves.
Lu (OH)3 +3OH- → [Lu(OH)6]3-

The electronic configuration of Gd+3 and Lu+3 are 4f7 and 4f14, for this ions total angular momentum is
zero i.e. there is no orbital contribution. Therefore, calculated and observed values of magnetic moment
are closest for this pair.

µobserved = µs + µl
µobserved = µs only if µl =0

285
Ground state term → 6D

2s+1=6
2s=5 => s =5/2 i.e. five unpaired electrons
For D, term L=2

Sm→ [Xe]4f6 5d0 6s2 , Sm+3 → [Xe]4f5 5d0 6s0
J=|L+S|…|L-S|
=|5+5/2|…. |5-5/2|
= 15/2 5/2
6
H15/2 , 6H5/2
Ground state term= 6H5/2
Eu = [Xe]4f7 5d0 6s2 , Eu= [Xe] 4f6 5d6 6s0
286
L=3+2+1+0-1-2-3
0 1 2 3
S P D F
J=|L+ S|……|L-S|
=|3+3|….. |3-3|
=6 0
7
F6 7 F0
Ground state term 7F0

Sm 4f6 5s0 6s2
Eu 4f7 5s0 6s2
Sm can accept one electron and become half field. So, it is better oxidant.

The retention of ion in exchanges column depends upon the size of ion. Smaller the size of cation,
stronger will be its binding ability. In cation exchanger column the aqueous solution of ion is passed
where binding ability depends upon hydrated radii.
K+ (aq) < Na+ (aq) < Li+ (aq)
Since, size of hydrated ion increases as shown above.
Therefore, binding ability decreases as K+ (aq) > Na+ (aq) >Li+ (aq)
Ag+(aq) show polarization effect, hence, has high binding ability.
Correct order : Ag+ > K+ > Na+ > Li+

Dipivaloylmethane, form chelats with lanthanides
287

2UO2+ (aq) + 4H+ (aq) → U+4 +UO2+2 (aq) + 2H2O
UO2+ disproportionates more easily than UO2+2 [correct ]
(B)U3O8 is most stable oxide of U. U3O8 is stable at high temperature [correct]
(C)[UO2(NO3) 2(H₂ O) 2] co-ordination number = 8 [incorrect]
(D)UO2+2 is linear [O=U=O] +2 [correct]

(NH4) 2[Ce(NO3) 6](Z)
(1) NO-3 behaves as bidentate ligand. Hence, C.N = 12
(2) Ce+4 has no unpaired electron hence dimagnetic not paramagnetic.
(3) Ce+4 has higher oxidation state hence behave as oxidising agent.
(4) (NH4) 2[Ce(NO3) 6] on reaction with Ph3PO gives [Ce(NO3) 4(Ph3PO)2] having . C.N.=10.
Hence correct statement.
OPPh3 = mono dentate ligand; NO3= bidentate

The Eu and Yb donate two electrons in their metallic bonding unlike other lanthanoids which donate
three electrons.
This is due to Eu+2 (4f7) and Yb+2 (4f14) stable configurations
Ln→Ln+3 + 3e-
Eu→ Eu+2 + 2e- (4f7) half filled stable kernel
Yb → Yb+2 +2e- (4f14) full filled stable kernel
Hence, they show abnormally larger sizes than other lanthanoids.
Eu =1.99Å , Yb=1.94 Å
288
(a) There is no good agreement between the calculated (µg = g J J + 1 B.M.) and experimental
magnetic moments for Eu+3 and Sm+3 ions because of low value of spin orbit coupling constant.
Therefore, the ground state and the first excited states become equally populated, due to the thermal
motion become equally populated due to thermal motion. Hence, the observed magnetic moment of Eu+3
at room temperature is higher than that calculated from spin-orbit coupling.
(b) Lanthanide oxides are predominantly basic in nature.
(c) The Sm(II) ion has 4f configuration. Thus, in Sm (II) 4f subshell is not half filled
(d) Since the chemical properties of the tripositive lanthanide ions (due to their similar size) they cannot
be separated easily by chemical method. Instead they can be separated by ion exchange chromatography.
[UO2(NO3)3 ]-1
Co-ordinate number is 8 and geometry is hexagonal bipyramidal.

Lande's splitting factor g is calculated as
J (J+1) +S(S+1)- L(L+1)
g = 1+
(J(J+1)
Ce+3 = f1
L=3
S=½
J=|L-S| for orbital less then half filled
J=|3-½|=5/2
289
5/2 (5/2+1) +1/2(1/2+1)- 3(3+1)

g= 1+
(×5/2(5/2+1)
g= 6/7
Pr+3 = f 3
L=3+2 =5
S= 1
J=|5-1|=4
4 (4+1) +1(1+1)- 5(5+1) 0
g= 1+ =
(×4(4+1) 1

A magic number is a number of nucleons (either protons or neutrons separately ) such that they are
arranged into complete shells , within atomic nucleus ,the seven most widely recoginized magic
numbers 2, 8, 20, 28, 50, 82 and 126 are magic number.

The calculated and observed magnetic moments of Eu+3 aqua complex are 0 and ~3.5 . The reason is
that with the spin orbital coupling constant is only about 230 cm . This means that the difference in
energy between the ground state and next excited state is small .So most of electrons goes to excited
state and paired .
Hence µ = J J + 1 = 0

(a) Lu(III) = [Xe] 4f14 5d0 6s0 hence diamagnetic
(b) EuI2 has metallic lustre
290
(c) Ce(IV) used as oxidising agent

(d) Tb(III) – f8 has pink colour

(A) Due to more expansion of 5f orbital actinoids has more tendency to release electron hence have
more tendency to show oxidation state greater than +3 compared to Lanthanoids
(B) Actinoids (III) show either f-d or f-f transition, but no d-d transition
(C) UO2+2 and PuO2+2 are stable
(D) All the actinoids have radioactive isotopes

Gd+3 ion show isotropic magnetic susceptibility

Pink → Sm(III)
Red → Eu(III)
Green → Tb(III)
Blue → Tm(III)
L=3 =F
S=3 2S+1=7
J= |L-S| =|3-3|=0
Hence, 7F0
Since, J=0 hence µ should be zero but due to population of higher J level µ >0. But as temperature
decreases population in excited J level decreases hence magnetic moment approaches to calculated value
i.e. zero.
291

In hexahydrate of gadolinium (III) chloride, six H₂ O molecules and 2Cl- ions coordinate to the metal
cation resulting in a coordination number of 8.
GdCl3.6H2O = [GdCl2(H2O)6]+ Cl-

The configurations and magnetic moment are
M+3 fn µ observed µ calculated
Gd+3 4f 7 7.97 7.94
Lu+3 4f 14 0 0
Tb+3 4f 8 9.8 9.7
Sm+3 4f 5 1.64 0.85
Eu+3 4f 6 3.36 0
• Gd+3 (f7) and Lu+3 (f14) follow spin only formula µ = 5

𝑛(𝑛 + 2)
• While for remaining µ(eff) = g 5 J(J + 1) is valid

Ac shows only +3 oxidation state because it achieve nearest noble gas configuration of Rn.
Lr shows only +3 oxidation state because it achieve fully filled [Rn] 5f14 configuration.

a.Lu+3 = Completely filled f14 configuration thus, no f-f transition.
b. For Tb+3, the main emissions responsible are 5D4 → 7Fn ( n = 6 - 0) with 5D4→ 7F5 the
strongest, whilst for Eu+3 , 5D0 → 7Fn are seen (n= 4-0) with the transitions to 7F0 , 7F1 and 7F2
the most useful
c. Overlapping J levels are observed for Sm+3

292
The value of 𝜇9:: can be calculated using formula; 𝜇9:: = 𝑔 𝐽(𝐽 + 1)

Where,
𝑆 𝑆 + 1 − 𝐿 𝐿 + 1 + 𝐽(𝐽 + 1)
𝑔 = 1 +
2𝐽(𝐽 + 1)
10
for f configuration
Here, S = 2, L = 6 and J = 8,
Solving for 𝑔 will give, 𝑔 = 1.25
Hence 𝜇9:: = 10.6

294
Chemical Bonding
CSIR JUNE 2011

- - -
1.Among SF4 , BF4 ,XeF4, and ICI4 , the number of species having two lone pair of electrons
central atom according to VSEPR theory is:
(a) 2
(b) 3
(c) 4
(d) 0
2. In the molecules H2O, NH4 and CH4

(a) The bond angles are same (b) The bond distances are same.
(c) The hybridizations are same (d) The shapes are same.
3. According to VSEPR theory, the molecule/ion having ideal tetrahedral shape is:
(a) SF4
(b) SO4-2
(c) S2Cl2
(d) SO2Cl2
4.The highest occupied MO in N2 and O2+ respectively are (take x-axis as internuclear axis)
(a) σ2px , π*2py
(b) π2py , π2pz
(c) σ*2px , σ 2px
(d) π*2py , π*2pz
5. The molecule with highest number of lone-pairs and has a linear shape based on VSEPR theory
is:
(a) CO2
(b) I-3
(c) NO-2
(d) NO+2
CSIR DEC 2011

6. The number of anti-bonding electrons in NO and CO according to MO theory are respectively.
(a) 1,0
(b) 2,2
(c) 3,2
(d) 2,3
7. Among the following pairs, those in which both species have similar structures are:
-
(A) N3 , XeF₂
- 2-
(B) [ICl4] , [PtCl4]
295
Chemical Bonding
+ -
(C) [ClF2] [ICl2]
(D) XeO3 , SO3
(a) (A) and (B) only
(b) (A) and (C) only
(c) (A), (B) and (C) only (d) (B), (C) and (D) only
8.Match list I (compounds) with list II (structures), and select the correct answer using the codes
given below.
List-I List-II
(A) XeO4 (i) square planar
-
(B) BrF4 (ii) tetrahedral
(C) SeCl4 (ii) distorted tetrahedral..
(a) (A-ii) (B-iii) (C-i)
(b) (A- iii) (B-i) (C-ii)
(c) (A-ii) (B-i) (C-iii)
(d) (A-i) (B-ii) (C-iii)
CSIR JUNE 2012

9.The size of the d orbitals in Si, P, S and Cl follows the order.
(a) Cl > S > P > Si
(b) Cl > P > S > Si
(c) P > S > Si >Cl
(d) Si > P > S >Cl
-
10.The total number of lone pairs of electrons in I3 is:
(a) Zero
(b) Three
(c) Six
(d) Nine
11. The strength of Pπ-dπ bonding in E-O (E = Si, P, S and Cl) follows the order
(a) Si-O>P-O>S-O>Cl-O
(b) P-O>Si-O>S-O>Cl-O
(c) S-O> C1-O>P-O>Si-O
(d) Cl-O>S-O>P-O>Si-O
12.The decreasing order of dipole moment of molecules is

(a) NF3 > NH3 >H2O
(b) NH3 > NF3 > H3O
(c) H2O>NH3 > NF3
(d) H2O > NF3 > NH3
296
Chemical Bonding
CSIR DEC 2012

-2 -
13.Which ones among CO3 , SO3 , XeO3 , and NO3 1 , have planar structure?
-
(a) CO3 2, SO3, and XeO3
-
(b) SO3, XeO3, and NO3
- -
(c) CO3 2, XeO3, and NO3
- -
(d) CO3 2, SO3, and NO3
14.When a hydrogen a is placed in an electric field along the y-axis, the orbital that mixes most
with the ground state 1s orbital is
(a) 2s
(b) 2px
(c) 2py
(d) 2pz
CSIR JUNE 2013

15. Among the compounds A-D, those which hydrolyse easily are
(a) NCl3
(b) NF3
(c) BiCl3
(d) PCl3
16. The number of lone-pairs are identical in the pairs

(a) XeF4 , CIF3
-
(b) XeO4 , ICl4
-
(c) XeO2F2 , ICl4
(d) XeO4 , CIF3
CSIR DEC 2013

17.Among the following, an example of a hypervalent species is
(a) BF3.OEt2
(b) SF4
-
(c) [PF6]
(d) Sb2S3
18. The molecule in which the bond order increases upon addition of an electron
(a) O2
(b) B2
297
Chemical Bonding
(c) P2
(d) N2
19.The energy of 2s and 2p orbitals is the same for

+2 +2 -
(a) Li (b) Li (c) Be d) H
20. If a homonuclear diatomic molecule is oriented along the Z-axis, the molecular orbital formed
by linear combination of px, orbitals of the two atoms is
(a) σ
(b) σ*
(c) π
(d) 𝜹
+
21. According to VSEPR theory, the geometry (with lone pair) around the central iodine in I3
-
and I3 ions respectively are
(a) tetrahedral and tetrahedral
(b) trigonal bipyramidal and trigonal bipyramidal
(c) tetrahedral and trigonal bipyramidal
(d) tetrahedral and octahedral
CSIR JUNE 2014

22. The correct non-linear and iso-structural pair is
-
(a) SCl2 and I3
+
(b) SCl2, and I3
-
(c) SCl2, and ClF2
+ -
(d) I3 and ClF2
23 . Structures of SbPh5 and PPh5 respectively are

(a) trigonal bipyramidal, square pyramidal
(b) square pyramidal, trigonal bipyramidal
(c) trigonal bipyramidal, trigonal bipyramidal
(d) square pyramidal, square pyramidal
24. The maximum bond order obtained from the molecular orbitals of a transition metal dimer,
formed as linear combinations of d-orbitals alone, is
(a) 3
(b) 4
(c) 5
(d) 6
CSIR DEC 2014

298
Chemical Bonding
25. The correct schematic molecular energy diagram for SF6 molecule is:
(a)
(b)
299
Chemical Bonding
(c)
(d)
26. The δ-bond is formed via the overlap of

(a) d x2-y2 and d x2-y2 orbitals
(b) d xz and d xz orbitals
(c) d xy and d xy orbitals
(d) d yz and d yz orbitals
CSIR JUNE 15
27. For the oxidation state(s) of sulphur atoms in S2O, consider the following
A. -2 and +4
300
Chemical Bonding
B. 0 and +2
C. +4 and 0
The correct answer(s) is/(are)
(a) A and B
(b) A and C
(c) B and C
(d) C only
+ +
28. The geometries of [Br3] and [I5] respectively, are
(a) trigonal and tetrahedral
(b) tetrahedral and trigonal bipyramidal
(c) tetrahedral and tetrahedral
(d) linear and trigonal pyramidal
CSIR DEC 2015

29.The structures of XeF2 and XeO2F2 respectively are
(a) bent, tetrahedral
(b) linear, square planar
(c) linear, see-saw
(d) bent, see-saw
30. The molecule C3O2 has a linear structure. This compound has
(a) 4σ and 4π bonds.
(b) 3σ and 2π bonds
(c) 2σ and 3π bonds
(d) 3σ and 4 πbonds.
31. Among the following, species expected to show fluxional behaviour are
-2
(A) [NiCl4] (tetrahedral)
(B) IF7 (pentagonal bipyramidal)
-3
(C) [CoF6] (octahedral)
(D) Fe(CO)5 (trigonal bipyramidal)
(a) B and C
(b) B and D
(c) C and D
(d) A and D
32.The correct statement among the following is

+ +
(a) N2 has higher bond order than N2 and hence has larger bond length compared to N2 .
+
(b) N2 has higher bond order than N2 and hence has larger bond length compared to N2
301
Chemical Bonding
+ +
(c) N2 has higher bond order than N2 and hence has higher dissociation energy compared to N2
+ +
(d) N2 has lower bond order than N2 and hence has lower dissociation energy compared to N2
energy.
- -
33.The number of lone pair(s) of electrons on the central atom in [BrF4] , XeF6 and [SbCl6] are
respectively
(a) 2, 0 and 1
(b) 1, 0 and 0
(c) 2, 1 and 1
(d) 2, 1 and 0
34. The ground state electronic configuration of C2, using all electron is
2 2 2 2 2 2
(a) σ1s σ1s* σ2s σ2s* σ2p π2p
2 2 2 2 2 2
(b)σ1s σ1s* σ2s σ2s* σ2p σ2p*
2 2 2 2 2 1 *1
(c) σ1s σ1s* σ2s σ2s* π2p σ2p σ2p
2 2 2 2 4
(d) σ1s σ1s* σ2s σ2s* π2p
CSIR JUNE 2016

35. Correct combination for π and π* orbitals in B2 molecule is
π π*
(a) Gerade Ungerade
(b)Ungerade Gerade
(c) Gerade Gerade
(d)Ungerade Ungerade
36. The correct shape of [TeF5]-1 ion on the basis of VSEPR theory is
(a) Trigonal bipyramidal
(b) Square pyramidal
(c) Pentagonal planar
(d) See-saw
37. The number of 3c-2e bonds present in Al(BH4)3 is-

(a) four
(b) three
(c) six
(d) zero
CSIR DEC 2016

38. The expected H-H-H bond angle in [H3]+ is
(a) 180°
302
Chemical Bonding
(b) 120°
(c) 60°
(d) 90°
39. The oxidation state of gold in the following complex is
(a) 0
(b) 1
(c) 2
(d) 3
40. The numbers of triangular faces in square antiprism, icosahedron and tricapped trigonal
prism (capped on square faces), respectively, are
(a) 8, 20 and 14
(b) 8, 20 and 12
(c)10,12 and 14
(d) 10, 12 and 12
CSIR JUNE 2017

41. Based on VSEPR theory, the predicted shapes of [XeF5]- and BrF5 respectively, are
(a) pentagonal planar and square pyramidal
(b) square pyramidal and trigonal bipyramidal
(c) trigonal bipyramidal and square pyramidal
(d) square pyramidal and pentagonal planar
CSIR DEC 2017

42. Among ClO3 , XeO3 and SO3 , species with pyramidal shape is/are?
(a) ClO3- and XeO3
(b) XeO3 and SO3
(c) ClO3- and SO3
(d) SO3
43. Geometries of SNF3 and XeF2O2 respectively, are

(a) square planar and square planar
(c) square planar and trigonal bipyramidal
303
Chemical Bonding
(d) tetrahedral and trigonal bipyramidal

(b) tetrahedral and tetrahedral
44. According to Bent's rule, for p-block elements, the correct combination of geometry around
the central atom and position of more electro-negative substituent is
(a) Trigonal bipyramidal and axial
(b) Triogonal bipyramidal and equatorial
(c) Square pyramidal and axial
(d) Square pyramidal and basal
45. Allred-Rochow electronegativity of an element is

A. directly proportional to the effective nuclear charge
B. directly proportional to the covalent radius
C. inversely proportional to the square of the covalent radius
D. directly proportional to the square of the effective nuclear charge
(a) A and B
(b) A and C
(c) B and C
(d) A and D
CSIR June 2018

-4
46. Dinuclear anion [I2(OH)2O8] has two bridging oxo groups. The geometry around each iodine
is-
1. Octahedral
2. Monocapped octahedral
3. Square pyamidal
4. Pentagonal bipyramidal
47. Removal of an electron form NO molecule results in

A. An increase in the ῡ (NO) in the IR spectrum
B. An EPR active species
C. Electrons in HOMOs being closer to the oxygen than to nitrogen 2p orbital's
D. Electrons in HOMOs being closer to the nitrogen than to oxygen 2p orbital's
1. A only
2. A and C
3. Band D
4. A. B, and C
48. Consider the nature of solvents in column I and the corresponding max for l in various
solvents given in column II. (for I, vapor axis 520 nm). Match column I with column II
304
Chemical Bonding
1.(a)-(i); (b)-(ii); (c)-(iii); (d)- (iv)

2.(a)-(iii); (b)-(iv); (c)-(ii); (d)-(i)
3.(a)-(i); (b)-(iii); (c)-(iv); (d)- (ii)
4. (a)-(iv); (b)-(iii); (c)-(ii); (d)-(i)
49. Identify the correct statements about the electro negativity of groups given below:
(A) CF3 group has greater value than that of NF2
(B) NH2 group has lower value than that of NF2
(C) OH group has greater value than that of NF2
(D) CH3 and C2H5 groups have almost similar values
Correct answer is
1. A. B and D
2. B and C
3. B, C and D
4. B and D
CSIR DEC 2018

50. Among SiCl4 , P(O)Cl3 , NF3 , trans-[SnCl4(py)2] (py-pyridine), those with zero dipole moment
are
(a) SiCl4, and NF3
(c) SiCl4, and trans-SnCl4(py)2
(b) SiCl4 , P(O)Cl3 , and trans-SnCl4(py)4
(d) NF3 and trans-SnCl4(py)2
51. The characters of LUMO and CN- and O2 respectively, are

(a) σg and πu
(b) π and σu
(c) πg and σu
(d) σu and πg
52. Arrange the following molecules in order of increasing fundamental vibrational frequencies
(a) O2-2 < O2-< O2 < O2+
(b) O2 < O2+ < O2- < O2-2
(c) O2-2 < O2-< O2+< O2
(d) O2+< O2 < O2- < O2+2
305
Chemical Bonding
CSIR JUNE 2019

-
53. O2 is
(a) having a shorter O-O bond length than that in O2
(b) a stronger oxidising agent than O2
(c) IR active
(d) unable to abstract proton from weak acids
54. Among the following, the correct statement about π-molecular orbitals (π -MOs) of benzene is
(a) Only the lowest energy MO is doubly degenerate
(b) Only LUMO is doubly degenerate
(c) Only HOMO is doubly degenerate
(d) Both the HOMO and LUMO are doubly degenerate.
55. Match the appropriate geometry on the right with each of the speices on the left
(A) FXeO(OSO2F) (I) linear
(B) FXeN(SO2F)2 (II) pyramidal
(C) XeO3 (III) T-shaped
(D) XeOF2 (IV) bent
(a) A-I, B-I, C-II, D-III
(b) A-I, B-1. C-II, D-IV
(c) A-IV, B-I, C-II, D-III
(d) A-1, B-IV, C-II, D-III
CSIR DEC 2019

56. The ion having the highest bond order is
(1)NO+
(2)O2+
(3)N2+
(4)C₂+
57. The magnitude of bond angles in gaseous NF3 , SbF3 and SbCl3 follow the order
(1)NF3 >SbF3 > SbCl3
(2)SbCl3> SbF3> NF3
(3)SbF3> SbCl3> NF3
(4)NF3 > SbCl3 > SbF3
58. The species for which the shapes (geometry) can be predicted by VSEPR theory is/are
(A) [PtCl4]2-
(B) [TeCl6]2-
(C) PF3 and SF6
Answer is
306
Chemical Bonding
(1)A and C
(2)B and C
(3)C only
(4)A and B
CSIR 2020
59. Choose the correct order of energy of 2σg and 1πu molecular
orbitals for B2 , C2 and O2 :
(a) 2σg >1πu for all the three
(b) 2σg >1πu for B2and C2 only
(c) 1πu >2σg for C2and O2 only
(d) 2σg > 1πu for B2and O2 only
60. As per the VSEPR theory, shapes of SO32- , CO32- and BrF4- are, respectively
(a) Trigonal pyramidal, trigonal planar and tetrahedral
(b) trigonal planar, trigonal pyramidal and square planar
(c) trigonal pyramidal, trigonal planar and square planar
(d) trigonal planar, trigonal pyramidal and tetrahedral
61. Consider the following statements for Allred-Rochow electronegativity (χAR):

(i) χAR is directly proportional to Zeff
(ii) χAR is inversely proportional to Zeff
(iii) χAR is inversely proportional to r(covalent).
(iv) χAR is inversely proportional to r2(covalent).
a. (i) and (iv)
b. (ii) and (iv)
c. (i) and (iii)
d. (ii) and (iii)
62. The total bond order between adjacent carbon atoms of benzene is
(a) 0.5
(b) 2
(c) 1.5
(d) 2.5
CSIR JUNE 2021
63. Among the following which set of molecular/ionic species all have a planar structure?
(a) 𝑩𝒓𝑭𝟑, 𝑭𝑪𝒍O𝟐 𝒂𝒏𝒅 [𝑿𝒆𝑭𝟓]−
(b) 𝑿𝒆𝑶𝟑, [𝑪𝒍𝑭𝟒]− 𝒂𝒏𝒅 𝑭𝑪𝒍O𝟐
307
Chemical Bonding
(c) [𝑪𝒍𝑭𝟒]−, 𝑩𝒓𝑭𝟑 𝒂𝒏𝒅 [𝑿𝒆𝑭𝟓]−

(d) 𝑭𝑪𝒍O𝟐, [𝑿𝒆𝑭𝟓]− 𝒂𝒏𝒅 𝑿𝒆𝑶𝟑
64. The total number of lone pairs of electrons on all the atoms in cyanogen azide and
thiocyanogen respectively, are
(a) 4 and 6
(b) 6 and 6
(c) 3 and 4
(d) 4 and 4
65. For [𝑯𝒈𝟐]2+ , the

bond order and the orbitals involved in bonding are, respectively
(a) one; s and s
(b) two; s and p
(c) one; p and p
(d) three; s and d
Correct Answers & Explanations

Explanation: Both XeF4 , ICl4- have 2 lone pair of electron. The shape being square plannar with
hybridization sp3d2

Explanation:
All three molecules have same hybridization sp3

Bond angles and bond distances are different, shapes are bent, pyramidal and tetrahedral respectively.
Explanation: SO4-2 is tetrahedral.
308
Chemical Bonding

Explanation : Taking x-axis as internuclear axis.
N2 = σ21s σ21s* σ22s σ22s* π22py π22pz σ22px
O2+ = σ21s σ21s* σ22s σ22s* π22px π22py σ22px π1*2pz π1*2py

Explanation: I-3 is linear with highest number of lone-pairs ( 9 lone-pairs )

309
Chemical Bonding
Number of electrons in antibonding MO of NO = 1

No electron is present in antibonding MO OF CO=0
So, number of antibonding MO is zero .

-
(A) N3 → linear, XeF₂, → Linear
+ -
(B) [ClF2] → Bent, [ICl2] → Linear
- 2-
(C) [ICl4] , → square planar, [PtCl4] → square planar
(D) XeO3→ Trigonal pyramidal, SO3→ Trigonal planar

Size of d-orbitals decrease with decrease in size of element. The decreasing order of size is
Si > P > S > Cl.
Therefore decreasing order of size of d-orbitals is Si> P > S >Cl.

Number of lone pair of electrons = 9

Smaller the internuclear distance between two atoms, stronger will be the π bonds. The increasing or
due of inter nuclear distance is Cl-O < S-O <P-O <Si-O Therefore strength of pπ –dπ bonding is Cl-O>
S-O>P-O>Si-O

310
Chemical Bonding
Therefore, order of dipole moment is H2O > NF3 > NH3

-
CO3 2 : sp²-hybridization (Trigonal planar)
SO3 : sp²-hybridization (Trigonal planar)
XeO3 :sp-hybridization. (Trigonal pyramidal)
NO3 :sp²-hybridization (Trigonal planar)
- -
CO3 2,SO3, and NO3 2, have planar structure.

40. When a hydrogen atom is placed in an electric field along the y-axis. The magnetic moment i.e
electron density will he oriented along y-axis and therefore the orbital that mixes most with the ground
state 1s orbital is 2py .

Among given compounds NF3 is not hydrolyse easily because, the more electro negative F atom
strongly attracts the electrons present in N atom and they are no longer available to get hydrolysed.
BiCl3 is not readily hydrolysed by water to give BiOCl.
BiCl3 +H2O→ BiOCl + 2HCl
But BiOCl redissolve in conc. HCI to produce BiCl, after evaporation. It has quasi molecular structure.
PCl3 is easily hydrolysed by water.

311
Chemical Bonding

-
More than 8 electrons in the valence shell of P in [PF6]

B2 = σ21s σ21s* σ22s σ22s* π12px π12py
456
B.O. = = 1
7
If an electron is added to B2, then will go bonding to π -orbital.
;56
B.O. becomes= = = 1.5 .
7

Li = 1s2 2s1 2p0
+2
Li 1s1 2s0 2p0 (hydrogen like)
+2
Be = 1s2 2s0 2p0
-
H = 1s2 2s0 2p0
Li has one electron in 2s and no electron in 2p hence the energies of 2s and 2p orbitals will be
different.
Li+2 has only one electron in 1s1 hence will have no screening effect
Therefore, 2s and 2p will have same energies.

If a homonuclear diatomic molecule is oriented the z-axis, then linear combination of pz orbitals of two
atoms form σ-orbitals.
The molecular orbitals formed by linear combination of px or py orbitals of two atoms is π.

+ -
Number of valence electrons in I3 central atom are 8 while in I3 are 10 and hence the geometries are
tetrahedral and trigonal bipyramidal.
312
Chemical Bonding

(I) SCl2 b.p.=2 l. p. =2 Stearic number (S)=4
-
(II) I3 b.p. = 2 l. p. =3 (S)=5
+
(III) I3 b.p. = 2 l. p. =2 (S)=4
-
(IV) ClF2 b.p. = 2 l. p. =2 (S)=4
Shapes of species are

SbPh5 is square pyramidal while PPh5 is trigonal bipyramidal.
This is due to size of central atom. 'Sb' is bigger than 'P', therefore favour square planar while small
sized 'P' favour trigonal bipyramidal

A maximum five 'd' orbitals can form bonding with each other

In the formation of SF6 the following atomic orbitals are involved.
313
Chemical Bonding
The 3s, 3p of 's' and 2pz of 'F' are mixed to give ten MO's. Calculations indicate that four of orbitals will
be bonding and four of orbitals will be bonding and four will be antibonding. The remaining two will be
non-bonding. There are 12 electrons to be filled in ten MO's. The first two can enter 1a1 and the next six
can in it. The remaining four fill the non-bonding pair of orbitals. Thus it gives 1a2 1t6 e4 gives as
configuration. This gives the molecular diagram of SF6, as
26. Correct answer is (a) & (c)

A δ -bond involves the overlapping of eight lobes by facewise overlapping. This can take place by ‘d’-
orbitals and ‘f’ orbitals. In 'd' orbitals following two possibilities are
Case-I: d x2-y2 + d x2-y2 → δ bond
Case-II: d xy + d xy → δ bond.
Both cases are reported in many examples like.

Case-I is reported in dimeric copper acetate (II)
-
Case-II is reported in Re2Cl8
Hence, options (a) and (c) are correct

314
Chemical Bonding
The structure of S2O show resonance as
Hence, the probable O.S. of 'S' are (0 and +2) from structure 'T' and (-2 and +4) from structure II.

+ +
[Br3] = Br. Br2
;>75?
S= = 4 = sp³
7
Therefore, geometry = tetrahedral.
+
[I5]
geometry = trigonal bipyramidal, sp³d hybridisation)

XeF2 ; S = steric number = @AB
B
=5
Therefore, G = Geometry = trigonal bipyramidal (TBP)
Hence, the shape linear Xe

XeO2F2 s= @AB
B
=5 Geometry =TBP

The structure of C3O2 (carbon suboxide) is
4σ and 4π
315
Chemical Bonding

In IF7 and Fe(CO)5 , the rearrangement is so fast that axial and equatorial ligands cannot be
differentiate by spectroscopy). The molecules in which rearrangement leads to configuration which are
chemically equivalent are called fluxional molecule.

+
The Mo configuration of N2and N2 are
2 2 2 2 2
N2 = σ2s σ2s* π2px π2py σ2pz
𝟖5𝟐
B.O.= =3
𝟐
+ 2 2 2 2 1
N2 = σ2s σ2s* π2px π2py σ2pz
𝟕5𝟐
B.O.= =2.5
𝟐
N₂→ N₂ (Bond order decreases)
33. correct option is (c)
3-
Note: The lone pair of [SbCl6] is steriochemically inactive and that of XeF6, is boderline of
stereochemically active and stereochemically inactive condition.

C2 = valence electron = 12
2 2 2 2 4
C2 = σ1s σ1s* σ2s σ2s* π2p
316
Chemical Bonding

B = σ21s < σ21s* < σ22s < σ22s* < π12px = π12py < σ2px
Centre of symmetry No centre of symmetry

4>E>?
[TeF5]-1 = = 6
7
Number of lone pair = 1
Structure is square pyramidal

The structure of [Al(BH4)3] is
317
Chemical Bonding
Thus, number of 3c-2e bond is equal =6
Each bond angle is 60°

Oxidation state of gold in this complex is 2

Number of triangular anti-prism are 8 , in icosahedron it is 20 and in tricapped trigonal prism (capped
on square faces) it is 14

318
Chemical Bonding

;>4×G>? 74
ClO3- = = = 3+1 =4 sp3 (Tetrahedral)
H H
H>4×7 74
Xe= = =3+1=4→sp3 (Tetrahedral)
H H
4>4×G 76
SO3 = = =3→sp2 (Trigonal planar)
H H

4>E>;×G G7
SNF3 = = = 4 = sp3 = Td
H H
H>4×7>;×7 G6
XeO2F2 = = == =4+1= 5=sp3d→TBP
H H
319
Chemical Bonding

According to Bent's Rule, 'more electro negative element occupy axial position in trigonal bipyramidal
geometry.

According to Allred-Rochow, electronegativity can be given as
0.3590𝑍NOO
𝑋= + 0.744
r7
where r2 = covalent radius.

The correct structure of dinuclear anion [I2(OH)2O8]-4 with two bridging oxo groups, is as shown below

According to MOT
NO→ σ21s < σ21s* < σ22s < σ22s* < π22px = π22py < σ22pz < π1*2pz = π*2py < σ2pz*
10 - 5
Bond order of NO = = 2.5
2
10 - 4
Bond order of NO+ = =3
2
Hence, as bond order increases v (NO+) increases and NO+ → EPR inactive as no unpaired electron
In NO+ HOMO is σ2pz that is close to more electronegative atom (Oxygen).

The energy difference between π* and σ* is very small and it absorbs at λmax =520 nm. When I2 is
dissolved in a non-donor solvent, there is no effect on energies of π* and σ* of I2 and it absorbs at λ max
=520 nm. Interaction of solvent donor orbital with the σ* ,I2 LUMO result in a lower occupied bonding
orbital and a higher uncoupled bonding orbital As a result the π*→ σ* transition for the I2 donor adduct
is shifted higher in a energy and lower wavelength.
Hence, electron donor < weak donor < strong donor
(i) The electronegativity of CF3 is less than NF2
(ii) NH2 group has less electronegative than NF2
(iii) OH group has less electronegative than NF2
(iv) CH3 and C2H5 group have almost similar value of electronegativity.
320
Chemical Bonding

According to MOT the LUMO of CN- and O2 respectively are πg and σu

As bond order increases, stretching frequency increases.
O2+= 2.5 , O2 = 2, O2- =1.5 O2+2 = 1

O2- → σ21s < σ21s* < σ22s < σ22s* < π22px = π22py < σ22pz < π2*2px = π1*2py
O2 → σ21s < σ21s* < σ22s < σ22s* < π22px = π22py < σ22pz < π1*2px = π1*2py
6-3
Bond order of O2- = = 1.5
2
6-2
Bond order of O2 = =2
2
Bond order of O2 is more than O2- thus, bond length of O2- is more than O2.
• The superoxide ion O2- is able to abstract proton from weak acids. It reacts with a proton or
proton donor to form HO2
O2- +HX → HO2 + X-
• The superoxide ion O2- is a stronger oxidising agent than O2
• O2- does not possess dipole moment thus, it is IR inactive.

The MO diagram of benzene is
Thus both HOMO and LUMO are doubly degenerate.

321
Chemical Bonding

The bond order can be calculated by molecular orbital theory
Molecule Bond Order
+
NO 3
O2+ 2.5
N2+ 2.5
+
C2 1.5
NO = σ 1s < σ 1s* < σ 2s < σ 2s* < π22px = π22py < σ22pz
+ 2 2 2 2
O2+ = σ21s < σ21s* < σ22s < σ22s* < π22px = π22py < σ22pz < π1*2pz = π1*2py
N2+ = σ21s < σ21s* < σ22s < σ22s* < π22px = π22py < σ12pz
C2+ = σ21s < σ21s* < σ22s < σ22s* < π22px = π12py
8-2
Bond order of NO+ = =3
2
8- 3
Bond order of O2+ = = 2.5
2
7- 2
Bond order of N2+ = = 2.5
2
5- 2
Bond order of C2+ = = 1.5
2

According to VSEPR theory as the size of central atom increases bond angle decreases. Hence, Bond
angle of NF3 > SbCl3 ,SbF3
Now, in between SbCl3 and SbF3 . 'F' is more electronegative and pull the bond pair towards itself due
to which bond angle FSbF decreases. The experimental bond angles are

•VSEPR theory is applicable for main group elements not for transition metal elements. Hence [PtCl4]2-
can't be explained.
322
Chemical Bonding
•Also VSEPR theory can not explain the structure of molecules which have stereochemically inactive
lone pair. In [TeCl6]-2 there is one such lone pair. It is perfectly octahedral and hence can't be described
by VSEPR theory.
•PF3 is having lone pair and is trigonal pyramidal according to VSEPR theory. And SF6 is perfectly
octahedral having no lone pair on 'S'.

In B2 and C2 , s-p mixing takes place thus, energy of 2σg is greater than 1πu whereas there is no s-p
mixing takes place in O2, thus, energy of 2σg, is less than that of 1πu

SO32-
Valence electrons = 6
6–2–2=2
↓ ↓ ↓
1σ 2σ [one
1π 2O- lone
1O pair]
Hybridisation=1+2+1 = 4 i.e. sp3
Shape = Trigonal pyramidal

BrF4-
7 – 3 = 4 + F-
↓ ↓ ↓
3σ [Two [One
3F lone coordinate
Pair] bond]
Hybridisation = 3 + 2 + 1 = 6 i.e. sp3d2
Shape = Square planar

CO32-
4-2-2=0
↓ ↓
1σ 2σ
1π 2O-
323
Chemical Bonding
1O
Hybridisation = 1 + 2 = 3 i.e. sp²
Shape = Trigonal planar

Allred-Rochow electronegativity (χAR):
χAR = (3590 z*/r2)+ 0.744
where, r = covalent radius (in pm), z* =effective nuclear charge

Firstly draw the molecular orbitals. Then add electrons and count the number of bonding and anti
bonding electrons.
The bond order of a bond is half the difference between the number of bonding and antibonding
electrons.
Bond order = 1/2 [Bonding-Anti-bonding]
The C-C sigma bonds.
Each C-C σ bond is a localised. It has 2 bonding electrons and zero non-bonding electrons.
σ Bond order = ½ (B-A) = ½ (2-0) = 1
The C-C π bond.
Benzene has 6 molecular π -orbitals of these, three are bonding and three are anti-bonding. The six π -
electrons go into the three bonding orbitals.
π Bond order= ½ (B-A) = ½ (6-0) = 3
This is the π bond order for 6 C-C bonds for one C-C π bond, Bond order = 3/6 =0.5
For a single C-C bond in Benzene, the total Bond Order σ + π = 1+ 0.5 =1.5

Applying VSEPR theory we can easily find out structures of the molecules
𝑩𝒓𝑭𝟑 has 3 bond pairs and 2 lone pairs, hence it’s geometry is TBP but structure is T-shaped
𝑭𝑪𝒍O𝟐 has 3 bond pairs and 1 lone pair, hence its geometry is Tetrahedral but structure is pyramidal.
[𝑿𝒆𝑭𝟓]− has 5 bond pair and 2 lone pairs, hence its geometry is Pentagonal bipyramidal but structure is
pentagonal plannar.
[𝑪𝒍𝑭𝟒]− has 4 bond pairs and 2 lone pairs, hence its geometry is Octahedral but structure is square
plannar.
𝑿𝒆𝑶𝟑 has 3 bond pairs and 1 lone pair, hence its geometry is Tetrahedral but structure is pyramidal.

The molecular structure are as follows
324
Chemical Bonding

Electronic configuration of Hg = 5d10 6s2
For Hg+ = 5d10 6s1
In order to form [Hg2]2+ there will be one sigma bond between two Hg+ atoms.

326
Acid and Bases
CSIR DEC 2011

1.The correct order of acidity among the following species is
+ +2 +2 +3
(a) [Na(H₂O)6] > [Ni(H₂O) 6] >[Mn(H₂O)6 ] > [Sc (H₂O)6]
+3 +2 +2 +
(b) [Sc (H₂O)6] > [Ni(H₂O) 6] > [Mn(H₂O)6 ] > [Na(H₂O)6]
+2 +2 +3 +
(c) [Mn(H₂O)6 ] > [Ni(H₂O) 6] > [Sc (H₂O)6] > [Na(H₂O)6]
+3 + +2 +2
(d) [Sc (H₂O)6] > [Na(H₂O)6] > [Ni(H₂O) 6] >[Mn(H₂O)6 ]
CSIR JUNE 2012

2. In the reactions (A) and (B),
n(H₂O) +Cl- → [Cl(H₂O)n] - ….. (A)
(H₂O)6+ Mg+2 →[Mg(H₂O)6]+2 ...... (B)
water behaves as
(a) An acid in both (A) and (B)
(b) An acid in (A) and a base in (B)
(c) A base in (A) an acid in (B)
(d) A base in both (A) and (B)
3. In the following reactions carried out in liquid NH3

Zn(NH2)2 +2KNH2 → K2[Zn(NH2)4]
K2[Zn(NH2)4]+ 2 NH4NO3 → Zn (NH2)2 +2 KNO3 + 4 NH3
KNH2 and NH4NO3 act respectively as
(a) Solvo-acid and solvo-base
(b) Solvo-base and solvo-acid
(c) Conjugate acid and conjugate base
(d) Conjugate base and conjugate acid
CSIR DEC 2012

4 .Match each item from the List-I (compound in solvent) with that from the List-II (its
behaviour) and select the correct combination using the codes given below.
List-I List-II
A. CH3COOH in pyridine (i) strong acid..
(ii) weak acid

B. CH3COOH in H2SO
C.HClO4 in H2SO4 (iii) strong base

D. SbF5 in HF (iv) weak base
327
Acid and Bases
(a) (A-i), (B-ii), (C-iii), (D-iv)

(b) (A-ii), (B-i), (C-in), (D-iv)
(c) (A-iii), (B-iv), (C-ii), (D-i)
(d) (A-iv), (B-ii), (C-iii), (D-i)
CSIR JUNE 13
5. The compound that will behave as an acid in H2SO4 is
(a) CH3COOH
(b) HNO3
(c) HClO4
(d) H2O
CSIR DEC 2013]

6. Among the following, the correct acid strength trend is represented by
(a) [Al(H2O)6]+3 < [Fe(H2O)6] +3 <[Fe(H2O) 6] +2
(b) [Fe(H2O) 6] +3 <[Al(H2O) 6]+3 < [Fe(H2O) 6] +2
(c) [Fe(H2O) 6] +2 < [Fe(H2O) 6] +3 < [Al(H2O) 6]+3
(d) [Fe(H2O) 6] +2 <[Al(H2O) 6]+3< [Fe(H2O) 6] +3
CSIR JUNE 15
7. Match the action of H2O2, in aqueous medium given in column A with the oxidation/reduction
listed in column B
A: action of H2O2 B: type of reaction
(1) Oxidation in acid (A) [Fe(CN)6]3- → [Fe(CN)6] 4-
(II) Oxidation in base (B) [Fe(CN)6]4- → [Fe(CN)6]3-
(III) Reduction in acid (C) MnO4- → Mn2+
(IV) Reduction in base (D) Mn2+ → Mn4+
(a) I-A, II-B, III-C, IV-D
(b) I-B, II-D ,III-C, IV-A
(c) I-C, II-D, III-B, IV-A
(d) I-D, II-A, III-C, IV-B
8. Water plays different roles in the following reactions.

(i) 2H2O+Ca → Ca+2 + 2OH- +H2
(ii) nH2O+ Cl → [Cl(H2O) n]-
(iii) 6H2O+Mg+2 → [Mg(H2O)6] +2
(iv) 2H2O+ 2F2 → 4HF+O2
The correct role of water in each reaction is,
(a) (i) oxidant, (ii) acid, (iii) base and (iv) reductant
(b) (i) oxidant, (ii) base, (iii) acid and (iv) reductant
328
Acid and Bases
(c) (i) acid, (ii) oxidant, (iii) reductant and (iv) base
(d) (i) base, (ii) reductant, (iii) oxidant and (iv) base
CSIR JUNE 2016

9. Which of the following react(s) with AsF5 in liquid BrF3 ?
(a) XeF6 only
(b) XeF6 and XeF4
(c) XeF6 and XeF2
(d) XeF4 and XeF2
10. Consider the following reactions:

N2O4
(A) NOCl +Sn
(B) NOCl+ AgNO3 →
(C) NOCl +BrF3→
(D) NOCl+ SbCl5 →
Reactions which will give [NO]+ as a major product are:
(a) A and B
(b) C and D
(c) A and C
(d) B and D
11. Among KF, SnF, and SbF4 , solute(s) that increase(s) the concentration of Br𝐅𝟑(𝟏
in BrF3 , is/are
(a) KF only
(b) KF and SnF4
(c) SnF4 and SbF5
(d) KF, SnF4 and SbF5
CSIR DEC 2016

12. For the reaction,
𝒈𝒊𝒗𝒆𝒔
HX (aq) +H2O(l) H3O+ + X-
the highest value of [X ] , when X- is
-
(a) OCl-
(b) F-w
(c) Cl-
(d) NO2-
329
Acid and Bases
13. Some molecules and their properties in liquid ammonia are given in columns A and B
respectively. Match column A with column B

(a) (A)- (i); (B)- (i); (C)- (iii); (D)-(iv)
(b)(A)-(i); (B)- (iii); (C)- (iv); (D)- (i)
(c) (A)-(iii); (B)-(iv); (C)- (i); (D)- (ii)
(d) (A)-(iv); (B)- (iii); (C)-(ii); (D) - (i)
CSIR JUNE 2017

14. The compound that gives a basic solution in HF is :
(a) AsF5
(b) PF5
(c) BF3
(d) BrF3
15. Match items in column A with items in column B:

(a)1-(A): II-(B); III-(C) IV-(D)
(b) I-(B); II-(D); III-(C); IV-(A)
(c) I-(C); II-(D); III-(B); IV-(A)
(d) I-(B); II-(D); III-(A); IV-(C)
330
Acid and Bases
CSIR DEC 2017

16. The reactions given below,
A Cl2+ H2O → HOCl+H3O+ + Cl-
B Cl2+ 2NH3 → NH2 Cl + NH4 + Cl-
are examples of
(a) disproportionation only
(b) disproportionation (A) and solvation (B)
(c) solvation (A) and disproportionation (B)
(d) solvalysis as well as disproportionation
CSIR JUNE 2018

17. The transformation are given in Column 1 and reagent in Column II. Match the items of
Column I with those of Column II
1. (a)-(i); (b)-(ii); (c)-(iii); (d)-(iv)

2. (a)-(ii); (b)-(iii); (c)-(iv); (d)-(i)
3. (a)-(iii); (b)-(ii); (c)-(i); (d) -(iv)
4. (a)-(iii); (b)-(i); (c)-(iv); (d)- (ii)
CSIR DEC 2018

18. Consider compounds PF5 , SbF5 , PH3 and SbH3 . The strongest acid and the strongest base
among these are, respectively
(a) PF5 and PH3
(b) SbF5 and PH3
(c) SbF5 and SbH3
(d) PF5 and SbH3
CSIR JUNE 2019

- -
19.The reaction of IO3 with I in aqueous acidic medium results in
(a) I2 and H2O
(b) I2 and H2O2
(c) IO- and H2O
(d) IO- and H2O2
331
Acid and Bases
20. Among the following reactions, those that are feasible in liquid NH3 are
(I) KNO3+AgCl →KCl+ AgNO3
(II) NH4Br + KNH2 → KBr + 2NH3
(III) Fe(CO)5 +2e- → [Fe(CO)4]2- + CO
(a) I, II and III
(b) I and II only
(c) I and III only
(d) II and III only
21. The cations formed upon dissolving SnF4 and AuF3 in liquid BrF3 separately, respectively are
(a) SnF3+ and BrF2+
(b) BrF2+ and AuF2+
(c) BrF2+ only
(d) SnF3+ and AuF2+
CSIR DEC 2019

22.Choose the equilibria from the following that are NOT favoured to go to right
gives
(A) As2S5 + 5HgO As2O5 +5 HgS
gives
(B) La2(CO3)3 + Bi2S3 La2S3 + Bi2(CO3)3
gives
(C) CaSO4+ CaS CdS+ CaSO4
gives
(D) BeF2 +HgI2 BeI2 + HgF2
(1)A and B
(2)A and C
(3)B and C
(4)B and D
23. Among SO2(OH)F, CH3CO2H , LiF and H2O, the compound(s) which behave(s) as a base in
liquid HF is/are
(1)CH3CO2H and LiF only
(2)LiF only
(3)SO2(OH)F and LiF only
(4)CH3CO2H , LiF and H2O
CSIR JUNE 2021
24. Identify the correct statement for the two reactions given below
(a) Xe and XeF4 both act as acids.

332
Acid and Bases
(b) Xe and XeF4 both act as bases.

(c) Xe acts as an acid and XeF4 acts as a base.
(d) Xe acts as a base and XeF4 acts as an acid.
25. Choose the correct statement(s) from the following:

(i) The trend in Lewis acidity among silicon halides is 𝑺𝒊𝑰𝟒 < 𝑺𝒊𝑩r𝟒 < 𝑺𝒊𝑪l𝟒 < 𝑺𝒊𝑭𝟒.
(ii) Tin(II) chloride can act as a Lewis acid and not as a Lewis base.
(iii) Aluminosilicates can display Brönsted acidity.
(a) (i) and (ii)
(b) (i) and (iii)
(c) (ii) and (iii)
(d) (ii) only
Correct Answers and Explanations

Higher the charge and smaller size of the central metal cation increases the acidic strength of hydrated
complex because it polarizes O-H band of H2O easily.
+3
In [Sc(H₂O)6] , Sc is in +3 oxidation state and has smallest size.
+3 +2
Therefore, in size of depositive ions increase in the order [Sc(H₂O)6] > [Ni(H₂O) 6] > [Mn(H₂O)6
+2 +
] > [Na(H₂O)6]

nH2O+ Cl-→[Cl(H2O)n]-
If negative end of O-H dipole approaches the Cl- ion, then there will be repulsion.
ion dipole interaction positive and of OH dipole approaches the Cl- ion and form Cl(H2O)n]-
Not stabilized. Thus H2O does not behave as a base 6H2O+Mg+2 → [Mg(H2O)6]+2
333
Acid and Bases
In this reaction Mg+2 behave as lewis acid and H2O behave as a ligand or lewis base.

CH3COOH+C5H5N : → CH3COO- + C5H5NH+ (solvo cation)
CH3COOH+H2SO4 →CH3COOH2+ + HSO4- (solvent anion)
HClO4+H2SO4 →ClO4-+H3SO4+ (solvent cation)→ [weak acid]
SbF5+2HF→ [SbF6]+H2F+ →[strong acid]

HClO4 behave as an acid in H2SO4 ,because HClO4 contain higher dissociation constant than that of
H2SO4.
HClO4, pKa, value -9
H2SO4 , pKa value -3,
HNO3 , pKa value -1,
CH3COOH , pKa value 4.7.
pKa value of HClO4 > pKa value of H2SO4

For aqua ion complex , acidity is more when (i) small size
(ii) greater charge.

(I) 2[Fe(CN)6]3- +H2O2+ OH- → 2[Fe(CN)6] 4- + 2H2O +O2
(alkaline medium) Reduction
(II) 2[Fe(CN)6] 4- +2H+ +H2O2 → 2[Fe(CN)6] 3- + 2H2O
(acidic medium) Oxidation
-
(III) 2MnO4 +6H +5H2O2 → 2Mn2+ +8H2O+5O2
+
(acidic medium) Reduction

In reaction (i)Water acting as an oxidant oxidizing Ca to Ca+2 getting itself reduced to H₂.
In reaction (ii) Water act as Lewis acid accepting elecron from Cl- which act as a ligand.
In reaction (iii) Water act as Lewis base donating electron to Mg+2 .
In reaction (iv) Water acting as an redutant reducing F to F-.
334
Acid and Bases
i) H₂O + Cl-1 = [Cl(H₂O)n] -1

Where, Cl = Base, H₂O = Acid
iii) 6H₂O +Mg+2 → octahedral complex shown below
Separation of XeF4 from a mixture involves preferential complexation of XeF2 and XeF6 and XeF4 is
then removed in vacuum

N2O4
(A) NOCl +Sn [NO]++ Cl- ([NO]+ is not majore product )
(B) NOCl+ AgNO3 → AgCl + N2O4 (Neutralization reaction)
(C) NOCl +BrF3→ [NO]+ + BrF4-
(D) NOCl+ SbCl5 → [NO]+ + SbCl6-

KF +BrF3 → K+ + BrF4-
SnF4 +2BrF3 → 2[BF]+ +[SnF6]-2
SbF5 +BrF3 → BrF2+ + [SbF6]-
This only KF increases the concentration of BrF4- in BrF3.

Due to more acidity of HCl it will undergo more ionization. Hence, concentration of Cl- will be
maximum.
335
Acid and Bases

Cl2 → solvolysis and disproportionation of Cl2 in NH3
Cl2 +2NH3 →NH2Cl + NH4+ + Cl-
S8 → undergoes disproportionation in liquid NH3
5S8 +16NH3 → 4SN- +4 S𝟔(𝟐 + 12NH4+
CH3COOH acts as strong acid in NH3
CH3COOH+NH3 → CH3COO- +NH4+
Molecules that do not behave as acid in water, may behave as weak acids in NH3
H2NCONH2 +NH3 → NH4+ + NH2CONH-

AsF5 + 2HF → [AsF6]- + [H2F]+
PF5 + 2HF →[PF6]- + [H2F]+
BF3 + 2HF → [BF4]- +[H2F]+
BrF3+ HF →[BrF2]+ + [HF2]-
BrF3 acts as base as it donate F- in HF

SbF5 + Br → [BrF2]+ + [SbF6]- →Lewis base behaviour of BrF3
[BrF2][SbF6] + Ag[BrF4]→ Ag[SbF6] + 2BrF3→Neutralization
KF + BrF3 →K+ + [BrF4]- → Lewis acid behaviour of BrF3
2BrF3 →[BrF2]+ +[BrF4]- → self-ionization

A → Cl2 + 2H2O → HOCl + H3O+ + Cl-
B → Cl2 + 2NH3 → NH4Cl+ NH4+ +Cl-
Above both reactions are example of solvolysis as well as disproportionation.

MnO4- + e- →MnO4-2 (By Na in liq. NH3)
Me3CH →Me3C+ (By super acids, only super acids attack C-H bond)
Ag + Au →Ag[AuF4]
H3PO4 +H+→P(OH)4+
(This reaction occurs in H2SO4 because in H2SO4 solvent, H3PO4 acts as a base)

SbF5 is strongest acid and PH3 is strongest base.

IO3- (aq) + 5I-(aq) + 6H+ (aq) → 3I2(aq) + 3H2O(l)

•When aqueous solution of AgNO3 is added to an aqueous solution of KCl, white ppt of AgCl is formed.
336
Acid and Bases
KCl+AgNO3 →AgCl + KNO3

White ppt
But in liquid NH3, the direction of the reaction is reversed.
AgCl + KNO3 → KCl+ AgNO3
• NH4Br + KNH2 → KBr + 2NH3
This reaction is neutralization reaction in liquid NH3
Ammonia solutions of alkali metals and alkaline earth metals are strong reducing agents.
Fe(CO)5 +2e- → [Fe(CO)4]-2 + CO

2BrF3 + SnF4 →(BrF2)2[SnF6]
Species formed in reaction are BrF2+ and [SnF6]-2
AuF3 + BrF3 → BrF2+[AuF4]-
Species formed in reaction are BrF2+ and [AuF4]-

This can be explained with the help of HSAB principle.
•Be+2 is hard acid hence favour hard base F-
•Also La+3 is hard acid, thus favour hard base CO3-2 . Therefore, process B and D are not feasible.
gives
La2(CO3)3 + Bi2S3 La2S3 + Bi2(CO3)3
HA HB ← HA SB
gives
BeF2 +HgI2 BeI2 + HgF2
HA HB ← HA SB

HOSO2F + HF → [H2F]+ + [SO3F]-
Acid
CH3CO2H+2HF → [CH3C(OH)2]+ + [HF2]-

Base
LiF + HF → Li+ [HF2]-

(Base)
H2O + HF → H3O+ + F-
(base)

In first reaction, Xe is acting as electron donor to become [Xe]+, hence as a base.
In second reaction XeF4 is accepting electron to become [XeF4]-, hence it is an acid.

337
Acid and Bases
Lewis acidity of silicon halides depends on electronegativity of halide groups

𝑙𝑒𝑤𝑖𝑠 𝑎𝑐𝑖𝑑𝑖𝑡𝑦 𝑜𝑓 𝑆𝑖𝑋L ∝ 𝐸𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑒𝑔𝑎𝑡𝑖𝑣𝑖𝑡𝑦 𝑜𝑓 𝑋
since, electronegativity order is F > Cl > Br > I , thus correct order of lewis acidity is 𝑺𝒊𝑰𝟒 < 𝑺𝒊𝑩r𝟒 <
𝑺𝒊𝑪l𝟒 < 𝑺𝒊𝑭𝟒. Hence Statement (i) is correct.
In statement (ii) SnCl2 is given, which is a Hypovalent compound, having incomplete octet and hence
will behave as Lewis Acid.
Aluminosilicates have general formula AlMxSiOy since there is NO H+ ion present thus there is no
chance of Brönsted acidity.

339
Bioinorganic Chemistry
[CSIR JUNE 2011]

1. The ligand system present in vitamin B12 is:
(a) Porphyrin
(b) Corrin
(c) Phthalocyanine
(d) Crown ether
2. Carboxypeptidase contains:
(a) Zn (II) and hydrolyses CO2
(b) Zn (II) and hydrolyses peptide bonds.
(c) Mg (II) and hydrolyses CO2
(d) Mg (II) and hydrolyses peptide bonds.
[CSIR DEC 2011]
3. Superoxide dismutase contains the metal ions

(a) Zn (II) and Ni(II)
(b) Cu(II) and Zn(II)
(c) Ni (II) and Co(III)
(d) Cu (II) and Fe(III)
4. Among the following drugs, the anticancer agents is:

(a) captopril
(b) chloroquine
(c) camptothecin
(d) ranitidine
5. The reduction of nitrogen to ammonia, carried out by the enzyme nitrogenase, needs,
(a) 2 electrons
(b) 4 electrons
(c) 6 electrons
(d) 8 elecrons
6. A metal ion that replace manganese (II) ion in mangano-proteins without changing its function,
is
(a) Fe (II)
(b) Zn (II)
(c) Mg (II)
(d) Cu (II)
340
7. In the bacterial rubredoxin, the number of iron atoms, sulfur bridges and cysteine ligands are
Fe atom sulfur bridge cysteine
(a) 4 4 4
(b) 2 2 4
(c) 2 2 2
(d) 1 0 4
[CSIR JUNE 2012]
8. The oxidation state of iron in met-hemoglobin is

(a) Three
(b) Two
(c) Four
(d) Zero
9.The changes (from A-D given below) which occur when O2 binds to hemerythrin are
(A) One iron atoms is oxidized
(B) Both the iron atoms are oxidized
(C) O2 binds to one iron atom and is also hydrogen bonded.
(D) O2 binds to both the iron atoms and is also hydrogen bonded.
(a) B and C
(b) B and D
(c) A and D
(d) A and C
10. In the photosynthetic systems the redox metalloproteins involved in electron transfer are
cytochrome (cyt, b), cytochrome bf complex (cyt bf) and plastocyanin (PC). The pathway of
electron flow is
(a) PC → cyt b→ cyt bf
(b) cyt bf→ cyt b→ PC
(c) cyt b→ cyt bf →PC
(d) PC→ cyt bf→ cyt b
[CSIR DEC 2012]
11.The correct set of the biologically essential elements is,

(a) Fe, Mo, Cu, Zn
(b) Fe, Cu, Co, Ru
(c) Cu, Mn, Zn, Ag
341
(d) Fe, Ru, Zn, Mg
12. Based on the behaviour of the metalloenzymes, consider the following statements
(A) In the enzymes, the zinc activates O2 , to form peroxide species.
(B) In the enzymes, the zinc activates H2O and provides a zinc boud hydroxide.
(C) In the oxidases, the iron activates O2, to break the bonding between the two oxygens
(D) Zinc ion acts as a nucleophile and attacks at the peptide carbonyl
The set of correct statements is,
(a) A and B
(b) B and C
(c) C and D
(d) A and D
13. Fe+2-porphyrins fail to exhibit reversible oxygen transport and cannot differentiate CO from
O2. However, the hemoglobin is free from both these pit falls. Among the following
(A) Fe+2 -porphyrins undergo 𝜇 -oxodimer formation and the same is prevented in case of the
hemo globin.
(B) Fe-CO bond strength is much low in case of hemoglobin when compared to the Fe+2
porphyrins.
(C) While Fe-CO is linear, Fe-O2 is bent and is recognized by hemoglobin
(D) The interlinked four monomeric units in the hemoglobin are responsible to overcome the
pitfalls.
The correct set of statements is
(a) A and B
(b) A and C
(c) C and D
(d) B and D
[CSIR JUNE 2013]

14. The coordination geometry of copper (II) in the type I copper protein plastocyanin is:
(a) square planar
(b) tetrahedral
(c) octahedral
(d) distorted tetrahedral
15. The metal ions present in the active site of nitrogenase enzyme co-factor are
(a) Fe, Mo
(b) Fe, W
(c) Fe, Cu
342
(d) Fe, Ni
16. For the metalloprotein hemerythrin, the statement that NOT TRUE is
(a) there are two ion centres per active site.
(b) both iron centres are hexacoordinated in the active state.
(c) one iron is hexacoordinated while the other is pentacoordinated in the active state.
(d) it is found in marine invertebrates.
[CSIR DEC 2013]
17. Patients suffering from Wilson's disease have

(a) Low level of Cu-Zn superoxide dismutase
(b) High level of Cu-Zn superoxide dismutase
(c) Low level of copper-storage protein, ceruloplasmin
(d) High level of copper-storage protein, ceruloplasmin
18. High dose of dietary supplement ZnSO4, for the cure of Zn deficiency
(a) reduces myoglobin
(b) increases iron level in blood
(c) increases copper level in brain
(d) reduces copper, iron and calcium levels in body
19. L-DOPA is used for treatment of-

(a) tuberculosis
(b) Parkinson’s disease
(c) diabetes
(d) cancer
20. Oxidised form of enzyme catalase (structure A); prepared by the reaction of [Fe(P)]+
(P = porphyrin) with H2O2 has green color because
III IV
(a) Oxidation state of iron changed from Fe to Fe
(b) Porphyrin ring is oxidized by one electron
(c) π –π* transition appears in the visible region
IV
(d) Fe is coordinated with anionic tyrosinate ligand in axial position.
[CSIR June 2014]

343
21. If an enzyme fixes N2 , in plants by evolving H2, the number of electrons and protons associated
with that, respectively are
(a) 6 and 6
(b) 8 and 8
(c) 6 and 8
(d) 8 and 6
22. Ozone present in upper atmosphere protects people on the earth

(a) due to its diamagnetic nature
(b) due to its blue colour
(c) due to absorption of radiation of wavelength at 255nm
(d) by destroying chlorofluoro carbons
23. Molybdoenzymes can both oxidize as well as reduce the substrates, because
(a) Mo(VI) is more stable than Mo(IV)
(b) Mo(IV) can transfer oxygen atom to the substrate and Mo(VI) can abstract oxygen atom from
the substrate
(c) Conversion of Mo(VI) to Mo(IV) is not favoured
(d) Mo(VI) can transfer oxygen atom to the substrate and Mo(IV) can abstract oxygen atom from
the substrate.
24. The cooperative binding of O2 in hemoglobin is due to

(a) a decrease in size of iron followed by changes in the protein conformation
(b) an increase in size of iron followed by changes in the protein conformation
(c) a decrease in size of iron that is NOT accompanied by the protein conformational changes
(d) an increase in size of iron that is NOT accompanied by the protein conformational changes
[CSIR DEC 2014]
25. The extent of π-electron conjugation in macrocyclic rings of (1) heme, (2) coenzyme B12 and (3)
chlorophyll follows the order
(a) (1)>(3) >(2)
(b) (1)>(2)>(3)
(c) (3) >(1)>(2)
(d) (2) >(1) > (3)
26. The number of histidine amino acid nitrogen atoms coordinated to bimetallic active site of
oxyhemocyanin, and oxyhemerythrin, respectively, are
(a) 2, 3 and 3, 3.
(b) 3, 3 and 2, 3
344
(c) 3, 3 and 2, 2
(d) 2, 4 and 3,2
27. Identify correct statements for mercury as an environment pollutant.

A. Carbanionic biomethylation converts it to MeHg+
B. Thiol group of cysteine has strong affinity for mercury
C. Mercury containing industrial catalyst release caused Minamata disaster
(a) A and B
(b) A and C
(c) B and C
(d) A, B and C
28. Under physiological condition, oxygen is binding to deoxyhemoglobin and deoxymyoglobin,

the binding curve and its pH dependence, respectively, are
(a) Sigmoidal and pH dependent; hyperbolic and pH independent
(b) Hyperbolic and pH independent:sigmoidal and pH dependent
(C) Sigmoidal and pH independent;hyperbolic and pH dependent
(d) Hyperbolic and pH dependent:sigmoidal and pH independent
29. Match the metalloproteins in column-A with their function in column-B

Column-A Column-B
I Oxyhemocyanin A. hydrolysis of C-terminal peptide bond
II Carbonic anhydrase B. Methylation
III. Cytochrome P450 C. Conversion of CO2 to H2CO3
IV. Carboxy-peptidase A D. oxdiation of alkene
E. oxygen storage
F. oxygen transport
(a) I-F: II-C; III - D; IV-A (c)I-F; II-B; III - C; IV-A
(b) I-E: II-C; III-A; IV-F (d) 1-E; II-D; III-C; IV-A
[CSIR JUNE 2015]
30. The biological functions of carbonic anhydrase and carboxypeptidase A, respectively, are
(a) interconversion of CO2 and carbonates and hydrolysis of peptide bond
(b) gene regulation and interconversion of CO2 and carbonates
(c) gene regulation and hydrolysis of peptide bond
(d) interconversion of CO2 and carbonates and gene regulation
345
31.The Fe-Nporphyrin bond distances in the deoxy and oxy-hemoglobin, respectively, are
(a) 2.1 and 2.0Å
(b) 2.0 and 2.0 Å
(c) 2.2 and 2.3Å
(d) 2.3 and 2.5Å
32.The total number of metal ions and the number of coordinated imidazole units of histidine in
the active site of oxy-hemocyanin, respectively, are
(a) 2Cu and 6
(b) 2Fe and 5
(c) 2Cu and 6
(d) Fe and 3.
[CSIR DEC 2015]
33. The biological functions of cytochrome P450 and myoglobin are, respectively
(a) oxidation of alkene and O2 storage
(b) O4 trasnport and O2 storage
(c) O2 storage and electron carrier
(d) electron carrier and O2 transport
34. Deoxy-hemocyanin is
(a) heme protein and paramagnetic
(b) colourless and diamagnetic
(c) O2 transporter and paramagnetic
(d) blue colored and diamagnetic
35. The resonance Raman stretching frequency (ⱽ o-o. in cm-1) of O2, is 1580. The ⱽ o-o for O2 in
bound oxy-hemoglobin is close to
(a) 1600
(b) 1900
(c) 800
(d) 1100
36. Match the metalloprotein in Column-A with its biological function and metal centre in
Column-B.
Column-A Column-B
(A) hemoglobin (I) electron carrier and iron
(B) cytochrome b (II) electron carrier and copper
346
(C) vitamin B12 (III) O2 transport and copper
(D) hemocyain (IV) Group transfer reactions and cobalt
(V) O2 storage and cobalt

(VI) O2 transport and iron

(a) A-VI, B-I, C-IV and D-III
(b) A-V. B-I, C-IV and D-III
(c) A-VI. B-V, C-I and D-II
(d) A-V, B-VI, C-II and D-IV
[CSIR JUNE 2016]
37. In the absence of bound globin chain, heme group on exposure to O2 gives the iron-oxygen
species -
38. Match the metal given in Column-A with its medicinal use as a compound in Column-B
Column-A Column-B
(A) Gd (I) Cancer
(B) Au (II) Maniac depression
(C) Pt (III) MRI contrast agent
(D) Li (IV) Arthritis
Correct match is
(a) A-II: B-III; C-IV: D-I
(c) A-III; B-IV; C-I; D-II
(b) A-IV; B-II: C-I, D-III
(d) A-I; B-II: C-III; D-IV
39. Correct combination of number and size of rings present in a metal ion-porphine complex
(including metal ion bearing chelate rings) is
(a) four 5-membered and four 6-membered
(b) two 5-membered and six 6-membered
(c) six 5-membered and two 6-membered
347
(d) five 5-membered and three 6-membered
40. In human body cisplatin hydrolyzes to diaqua complex and modifies the DNA structure by
binding to
(a) N-atom of guanine base
(c) N-atom of adenine base
(b) O-atom of cytosine base
(d) O-atom of thymine base
[CSIR DEC 2016]
41. In the catalytic hydration of CO2 by carbonic anhydrase, CO2 first interacts with
(a) OH group of the active site of the enzyme and then with zinc
(b) H2O of the active site of the enzyme and then with zinc
(c) zinc of the active site of the enzyme and then with OH group
(d) zinc of the active site of the enzyme and then with H2O
42. The number of inorganic Sulphur (or sulphide) atoms present in the metalloprotein active sites
of rubredoxin, 2-iron ferredoxin and 4-iron ferredoxin, respectively, are
(a) 0, 2 and 4
(b) 2, 4 and 3
(c) 0, 4 and 2
(d) 0, 2 and 3
43. From the following transformations,

A. Epoxidation of alkene
B. Diol dehydrase reaction
C. Conversion of ribonucleotide-to-deoxyribonucleotide
D. 1, 2-carbon shift in organic substrates
those promoted by coenzyme B12 are

(a) A and B
(b) B, C and D
(c) A , B and D
(d) A, B and C
44. Match the items in column A with the appropriate items in column B
Column A Column B
a.Metallothioneins i. Cis –[Pd(NH3)2Cl2]
348
b.Plastocyanin ii. Cysteine rich protein

c.Ferritin iii. Electron Transfer
d.Chemotherapy iv. Iron Transport
v. Iron Storage
vi. Carboplatin

(a) (A) - (i); (B) - (iii); (C) - (v); (D) - (iv)
(b) (A) - (i); (B) - (iii); (C) - (iv); (D) - (i)
(c) (A) - (i); (B) - (iii); (C) - (v); (D) - (vi)
(d) (A) - (iii); (B) - (v); (C) - (vi); (D) - (ii)
45 . Match the species in column X with their properties in column Y

Column-X Column-Y
(1) Heme A (i) oxo-bridged, Mn4 cluster
(2) Water splitting enzyme (ii) tetragonal elongation
(3) [Mn(H2O)6]+2 (iii) Predominantly, π→π*, electronic transitions
+2
(4) [Cr(H2O)6] (iv) d→d spin-forbidden transitions
(v) tetragonal compression
(a) (1)-(iii), (2)-(i), (3)-(v), (4)-(ii)
(b) (1)-(iii), (2)-(i), (3)-(iv), (4)-(ii)
(c) (1)-(v), (2)-(iii), (3)-(iv), (4)-(ii)
(d) (1)-(iii), (2)-(i), (3)-(iv), (4)-(v)
[CSIR JUNE 2017]
46. The resonance Raman stretching frequencies (in cm-1) of the bound O2 species in oxy-
hemerthyrin and oxy-hemoglobin, respectively, are
(a) 850 and 1100
(b) 750 and 850
(c) 850 and 850
(d) 1100 and 850
47. In vitro reaction of an excess of O2 with free heme B in aqueous medium the end product is
(a) hematin
(b)[O2--Fe(III)-protoporphyrin-IX]
(c) heme B(O2)
(d)oxoferrylprotoporphyrin-IX cation radical
48. Consider the following statements for metallothioneins:

349
A. the contain about 30% cysteine residues

B. they prefer to bind soft metal ions such as Cd(II), Hg(II) and Zn(II)
C. they are involved in electron transfer reactions
D. they are low molecular weight proteins
Correct statements are
(a) A, B and C
(b) A, B and D
(c) A, C and D
(d) B and C
49. Consider the following statements for deoxy-hemerythrin and deoxy-hemocyanin:

A. they are involved in O2 transport in biological systems
B. they contain two metal ions in their active site
C. active site metal centres are bridged by amino acid residues
D. they prefer to bind only one O2 per active site
(a) A, B and D
(b) A, C and D
(c) B, C and D
(d) A and C
[CSIR DEC 2017]
50. The correct statement for cytochrome c is

(a) It is a non-heme protein
(b) The coordination number of iron in cytochrome c is five
(c) It is a redox protein and an electron carrier
(d) It can store or carry dioxygen
51. The active site structure for oxy-hemerythrin is:

350
52. The number of inorganic sulfides in cubane like ferredoxin and their removal method,
respectively, are
(a) eight and washing with an acid
(b) four and washing with a base
(c) eight and washing with a base
(d) four and washing with an acid
[CSIR JUNE 2018]
53. For the catalytic activity of Cu and Zn containing enzyme, superoxide dismutase. What is /are
the correct statement (S)?
(A) Cu and Zn both are essential
(B) Only Cu is essential
(C) Zu is essential and Cu may be replaced by any other divalent metal atom
(D) Zn may be replaced by any other divalent metal atom
1. (A) only
2. (C) Only
3. (D) Only
351
4. (B) and (D)
54. Consider the following statements for the oxygenation of hemocyanine:

(A) Oxidation state of both copper atoms changes by two
(B) It becomes intense blue from colorless
(C) Dioxygen is reduced to O2-2
(D) The µ-ղ 2 : ղ 2 bond forms between each oxygen and copper atoms.
The correct statements are:
1. (A) and (C)
2. (B) and (C)
3. (A), (B) and (C)
4. (B), (C) and (D)
55. Choose the correct set of statements for cis-platin.

(A) It can be prepared from K2[PtCl4].
(B) It can be prepared from [Pt(NH3)4Cl2.
(C) In its preparation, the observed trans effect for Cl- is greater than that of NH3
(D) In blood it stays in equilibrium with cis-[Pt(NH3)2Cl(H2O)]+
(E) In DNA strand, it binds to two adjacent cytosine bases.
The correct set is
1. A, C and D
2. A, C, D and E
3. B, C and D
4. B, C, D and E
[CSIR DEC 2018]
56. The chelate rings made by macrocyclic ligand in vitamin B12 are
(a) One five-membered and three six-membered
(b) Two five-membered and two six-membered
(c) Three five-membered and one six-membered
(d) Four six-membered
57. Match the items given below in the three columns:
Correct matches:
(a) A-III-Z, B-I-Y, C-II-X
352
(b) A-II-Y, B-I-X, C-III-Z

(c) A-III-Y, B-I-Z, C-II-X
(d) A-I-X, B-II-Y, C-III-Z
[CSIR JUNE 2019]
58. The metal transferred by bacteria and fungi using siderophores/siderochromes is

(a) Mo
(b) Cu
(c) Fe
(d) Zn
59. The correct match for the compounds in Column-I with the property in Column-II is
Column-1 Column-II
(P) Dichlorodifluoromethane (I) Anti-inflammatory
(Q) Sulfadiazine (II) Insecticidal
(R) Cortisone (III) Antibacterial
(S) Hexachlorobenzene (IV) Ozone layer depletion
(a) P-11, Q-I, R-IV, S-III
(c) P-I, Q-III, R-II, S-IV
(b) P-IV, Q-1, R-II, S-III
(d) P-IV, Q-III, R-I, S-II
60. Consider the following statements with respect to Cytochrome P-450

(A) It has histidine coordinated to iron centre
(B) It is a membrane bound metalloenzyme
(C) It has Fe(III) ion in the resting state of the enzyme
(a) A, B
(b) A, C
(c) B, C
(d) A only
61. Consider the following transformation, reactions in the context of co-enzyme B12
(A) 1, 2-Carbon shift
(B) Hydration of CO2
(C) Benzene to phenol
(D) dimethyl sulfide to demethyl sulfoxide
The correct statement(s) for co-enzyme B12 is/are
(a) A, C, D
(b) A, B only
353
(d) A only
(c) B, C only
[CSIR DEC 2019]
62. Choose the correct statements for oxymyoglobin and cytochrome P450 (resting state) from the
following:
A. Both contain dianion of protoporphyrin-IX
B. They have same fifth-ligand bonded to metal centre from the protein backbone
C. They contain single active site
D. They contain metal ion in +3 oxidation state
Answer
(1)A. Band C
(2)A, C and D
(3)A. B and D
(4)Band C only
63. The correct match for the drug molecules in the Column A with their medicinal use in Column
B is
(1)P-i; Q-ii; R-iii

(2)P-ii; Q-i; R-iii
(3)P-iii; Q-i; R-ii
(4)P-i; Q-iii; R-ii
354
64. Complex(es) which has/have unpaired electron(s) that is equal to that of iron center in
oxymyoglobin is/are
A [Fe(ox)3]3-
B. [Fe(CN)6]3-
C. [NiCl4]2-
D. [Cu(NH3)4]2+
(Given: ox oxalato)
Correct answer is
(1)A and B
(2)B and D
(3)C only
(4)C and D
65. Match Column I , II and III

(1)A-iii-Y, B-i-Z ,C-ii-X
(2)A-iii-Y, B-ii-X, C-i-Z
(3)A-ii-X, B-i-Y, C-iii-Z
(4)A-i-X, B-iii-Z, C-ii-Y
[CSIR 2020]
66. The complex (es) showing activity against cancerous cells is/are
1. (a) only
2. (a) and (b) only
3. (a) and (c) only
355
4. (a), (b) and (c)
67. During the binding of O₂ to myoglobin (consider 'heme' in xy-plane), the molecular orbital of
O₂ and atomic orbital of Fe involved in the formation of the ϭ-bond is
(a) π* and dz2
(b) π* and dxz
(c) π and dxz
(d) π and dz²
68. In the catalytic cycle of Cytochrome P450 , the generation of [(porphyrin)+●FeIV(O)] from
[(porphyrin)FeIII(OOH)] involves
(a) One electron oxidation of [(porphyrin)FeIII(OOH)]
(b)Formation of the intermediate [(porphyrin)FeIV(OH)]
(c) Homolytic O-O cleavage of [(porphyrin)FeIV(OOH)]
(d) Heterolytic O-O cleavage of [(porphyrin)FeIII(OOH)]
[CSIR JUNE 2021]
69. Match the items of column I with the applications given in column II
(a) a–iii; b–iv; c–i; d–ii

(b) a–i; b–iii; c–ii; d–iv
(c) a–ii; b–i; c–iv; d–iii
(d) a–iv; b–ii; c–iii; d–i
70. Match the iron and copper proteins with biological function in the table below:
The correct matches are

(1) A-ii-Z, B-iii-X,C-i-Y
(2) A-ii-Z, B-i-X, C-iii-Y
(3) A-iii-Y, B-i-Z,C-ii-X
(4) A-i-Y, B-iii-Z, C-ii-X
356
71. In 3-iron ferredoxins, the number of sulfide bridges and cysteinyl ligands, respectively, are:
(a) 3, 3
(b) 4, 3
(c) 3, 4
(d) 4, 4
72. Which of the following statements for rubredoxin,

A. 𝑭𝟐+ center has a tetrahedral geometry.
B. Reduced form of iron is diamagnetic.
C. 𝑭𝒆𝟐+ center undergoes Jahn-Teller distortion.
D. It is a [2Fe–2S] cluster. are correct?
(a) A, B and C
(b) A, C and D
(c) C and D only
(d) A and C only
1. Correct Option (b)

Vitamin B12 molecule is built-around a Corrin ring containing cobalt (III) atom.

Carboxypeptidase enzyme contains Zn+² ion and it cleaves (hydrolyses) the carboxy terminal amino
acid from a peptide chain.
357

Camptothecin, an quinolone alkaloid, is used as a chemotherapeutic agent in the treatment of leukemia

N₂+ 8H+ +8e- +16 ATP → 2NH3 +H2 +16ADP+16Pi

EPR studies show that,Mn2+ can replace Mg2+ in nucleic acid processing enzymes

358
Hemoglobin met-hemoglobin

NAD+←Biological reductant
↓
Flovoprotein
↓
cyt b→ cyt bf → PC

Fe= Hb & Mb cytochromes
Mo= nitrogen fixation
Cu= hemocyanin
359
Zn= metalloezymes

Because zinc is a Lewis acid and hence,
So, correct option is (b)

However, oxidase are enzyme that catalyse the reduction of O2→ H2O or H2O2 .
O₂(g) + 4e- +8H+ (inside) →2H2O(l) + 4H+ (outside)

Free heme (i.e. without globular protein chain) it foms 𝜇 -oxodimer) i.e.
µ-oxo-dimer (hematin)
which is unable to bind O2

The coordination geometry of copper (II) in the type I copper protein plastocyanin is distorted
tetrahedral

Nitrogenase enzyme cofactor contains Fe, Mo also known as Iron-molebdenum cofactor.

360
Hemerythrin, one iron centre is penta coordinated and other is hexacoordinated and iron exist at
peractive site found in marine invertebrates.

Wilson's disease is caused by excess accumulation of Cu in the body. Thus the reason being low level of
copper-storage protein, ceruloplasmin.

Prolonged use of ZnSO4, for the cure of Zn deficiency, reduces the amount of copper, iron and calcium
levels in body.

l-DOPA, also known as levodopa and l-3,4-dihydroxyphenylalanine, it crosses the protective blood-
brain barrier, whereas dopamine itself cannot. Thus, l-DOPA is used to
increase dopamine concentrations in the treatment of Parkinson's disease and dopamine-responsive
dystonia.

Catalase is a tetramer of four polypeptide chains covering 500 amino acids.
It works as H2O2+ Fe (III)-E → H₂O+O=Fe (IV) - E
H₂O₂+O= Fe(IV) – E+ → H₂O + Fe(III)-E + O₂
The colour arises as Fe(III) changes into Fe(IV).

The chemical reaction involved is shown below:
N2 +8H+ +8e- +16 ATP → 2NH3 +H2 +16ADP+16Pi

Ozone is a diamagnetic gas which is of dark blue coloured due to absorption of red light.
(λ=557 and 602 nm)
361
Ozone depletion discovered by J.C. Farman over Halley Bay in Antarctica.

Ozone also show strong absorption in λ =255 UV which is good for earth, it act as a green house ,
sunlight can come in but it can not go out .
'UV-b' is most dangerous, would damage the DNA of all living beings.
Ozone protects earth by keeping it warm .

Molybdoenzymes containing Molybdenum as the central metal, since it exists in two stable oxidation
states (IV) and (VI), thus it can transfer oxygen atom to substrate as well as it can abstract oxygen atom
from the substrate.

The movement of iron atom and imidazole side chain of histidine toward the porphyrin plane results in
breaking of some of the salt bridges. The breaking of these salt bridges reduces the strain in hemoglobin
molecule. Therefore, the oxyform of hemoglobin is called relaxed state (i.e., R state). The T form of
deoxyhemoglobin discourages the addition of first dioxygen molecule.
The bonding of one dioxygen molecule to a subunit of hemoglobin reduces the steric hindrance in the
other subunits (due to breaking of salt bridges) and therefore encourages the third as well as fourth
subunits. This is called cooperative mechanism

Total number of π-electrons in microcyclic rings of heme, coenzyme B12 and chlorophyll is
Heme=11 π electrons in microcyclic ring
Coenzyme B12= 5 π electrons in microcyclic ring
Chlorophyll= 10 π electrons in microcyclic ring
Check-out below images.
Chlorophyll, 10 π electrons in
HEME, 11 π electrons in microcyclic ring
microcyclic ring
362
Vitamin B12, 5 π electrons in

microcyclic ring

In 1956, in Japan minamata disater had been broken out in coastal area. This is a neurological syndrome
caused by mercury pollution. The Hg+2 get converted into MeHg+ by carbonic biomethylation. Which
form strong bonding with thiol(-SH) group of protein having cysteine amino acid. Hence, A, B and C
are correct.
Myoglobin is pH independent .
Lungs (gills) Hb+ 4O2 → (HbO2) 4

Tissues Hb(O2) 4 +4Mb → 4MbO2 + Hb
363
pH dependent shown by hemoglobin is known as Bohr effect (binds one H+ for every dioxygen
molecules)

Oxyhemocyanin stables as oxygen carrier.
Carbonic anhydrase
Carbonic anhydrase converts CO2 to H2CO3
Cytochrome P450 oxidizes alkene to epoxide.
Carboxy peptidase A catalyzes the hydrolysis of C-terminal peptide bond.

The carbonic anhydrase enzyme that catalyst the rapid interconversion of carbon-dioxide and water to
bicarbonate and protons (and vice versa).
CO2+H2O→H2CO3 (in tissue high CO2 concentration)
HCO3- + H+→H2CO3→→CO2 + H2O (in lungs and nephronse of kidney)
Hydration occur in blood at high pH values.
Dehydration occur in lungs at low pH values.
Carboxypeptidase A is a pancreatic exopeptidase that hydrolise peptide bond of C terminal.
Where, Rʹ =Arg, Lys, and Ornithine

Deoxy . Hb Oxy Hb
Fe+2 HS Fe+2 LS
364
t2g4 eg2 t2g6 eg0

Fe is above the plane which Fe is fitted well inside the plane thus
tends to increase the Fe-N distance . reducing Fe-N bond distance.

Oxy-hemocyanin are proteins that transport oxygen throughout the bodies of some invertebrate animals.
These metalloprotein contain two copper atoms that reversibly bind a single oxygen molecule (O₂).
The total of six coordinated imidazole units of histidine present in the active site of oxy-hemocyanine.

Myoglobin is found in tissue and store the oxygen in tissue transported by Haemoglobin ,it contain
high-spin five coordinate Fe(II), reacts readily & reversibly with O2 to produce a low-spin Fe(II)-O2
complex [ storage of O2]
Cytochrome P450 haem containing monooxygenases, catalyses the insertion of oxygen in substrate ,
oxidation of 5-exoposition of camphor, oxidation of alkene etc.
34. Correct option is (b).

In deoxyhaemocyanin Cu is in Cu(I) state i.e. have d10s0 configuration therefore it colourless and
diamagnetic. Diamagnetism is due absence of unpaired electrons and colourless is due to no d-d
transition as all the orbitals are filled.
365
35. Correct option is (d).

O2 in free state, 𝜈()( = 1580 cm-1 when O2 bound to hemoglobin, it makes strong coordinate bond with
Fe of hemoglobin and O-O bond strength decreases slightly, so in oxy-hemoglobin, 𝜈()( = 1100 cm-1.
36. Correct option is (a).

Hemoglobin - O2 trasnport & iron
Cytochrome b- Electron carrier & iron
Vitamin B12- Group transfer reactions & cobalt
Hemocyanin - O2 transport & copper

Absence of globin chain following reaction is occur
PFeII + O2 →PFeII-O2 + FeIIP → P-FeIII-O-O-FeIII-P
234 (66)
2PFeIV =O PFeIII -O-FeIII-P
reversible
(Haematin)

Pt- complex used as anticancer drug
Au-complex used as anti arthritis agent
Gd-complex used in MRI as contrast agent due to their strong paramagnetic behaviour
Li-complex used in Maniac depression

Structure of m-porphyrine complex can be shown as
Here, (A) represents = five membered ring

(B) represents = six membered ring.
Thus, these are four 5-membered ring and four-6-membered ring.

cis-platin modifies the DNA structure by binding to N-7 nitrogen atom of guanine base.
366

In carbonic anhydrase OH group first attack on CO2 and then CO2 interact with Zn.
Here, step (2) shows attack of OH group with CO2, the product formed after step (3) shows later
interaction of CO2 with Zn metal.

367
Number of inorganic sulfur (sulfide) which do not belong to protein chain in ruberdoxin, 2-ferredoxin
and 4- ferredoxin are 0, 2, 4 respectively.

Co-enzyme B12 catalyses dehydration, 1, 2-carbon shift reaction in organic substrates and conversion of
ribonucleotide to deoxyribonucleotide.

Metallothionines → Cystein rich protein
Plastocyanin →Electron Transfer
Ferritin→ Iron storage
Chemotherapy→ Carboplatin

Heme A → Iron porphyrin →Colour due to π-π* water splitting enzyme contains bridged Mn4 cluster
[Cr(H2O)]+2 → t32g e1g → Tetragonal elongation

In oxyhemerythrin ῡO-O = 850 cm-1
In oxyhemoglobin ῡO-O = 1100 cm-1
47. Correct option is (a).

368

Metallothioneins are cystein rich, low molecular weight protein. Due to soft sulfur centre they prefer to
bind.

Both deoxyhemerythrin and deoxy hemocyanin are O2 transport protein in biological system. Both
contain two metal ion at active site and they bind only O2 per active site.

Cytochrome-c shows redox reaction and it is an essential component of electron transport chain.
whereas it is carriers of one electron and does not bind oxygen

In oxyhemerythrin, both the Fe are present as Fe(III) and there is presence of hydrogen bonding and
dioxygen bind to only one Fe.

Cubane like ferredoxin is Fe4S4 . It has four inorganic sulfide which can be removed by treatment with
acid.
H+
Fe4S4 Fe4+8 + 4H2S

The Cu ion is essential that can not be replaced by other metal atom while retaining activity. On the
other hand, the Zn+2 ion can be replaced by other divalent metals atom such as Co or Cd with retention
of most of the activity.
(1) In oxygenation of hemocyanin each Cu atom is oxidized by one.

369
(II) It becomes intense blue from colourless due to LMCT (O2-2 to Cu+2)
(III) O2 is reduced to O2-2 because each Cu is oxidized by one.
(IV) The O2-2 binds to two Cu atoms in the µ-ղ2 : ղ2 manner.
Trans effect of Cl- > NH3

In blood it stays in equilibrium with cis-[Pt(NH3)2Cl(H2O)]+
In DNA stand, cis-platin binds to two adjacent guanin bases (Not to cytosine bases)

Oxymyoglobin → O2- →1105 cm-1
Oxyhemocyanin → ղ2 : ղ2O2-2 →803 cm-1
Oxyhemerythrin → HO2- → 844 cm-1

Siderophores/siderochromes are small, high-affinity iron-chelating compounds secreted by micro
organisms such as bacteria and fungi and serving to transport iron across all membranes.

(P) Dichlorodifluoro methane →(iv) Ozone layer depletion
(Q) Sulfadiazine→ (iii)Antibacterial
370
(R) Cortisone→ (i)Anti-inflammatery

(S) Hexachlorobenzene→ (ii)Insecticidal

Cytochrome P-450 is a membrane bound metalloenzyme. The function of most cytochrome P-450
enzyme is to catalyze the oxidation of organic substrate. In the active site of cytochrome P-450, iron is
in +3 oxidation state and it is in octahedral geometry whereas the basal plane is composed of four N
atoms from the porphyrin ring, fifth position is occupied by a cysteine moiety and sixth position is
occupied by H2O molecule.

Coenzyme Vit-B12 was the first organometallic compound discovered in living systems. This coenzyme
catalyses 1, 2-rearrangement.
•Coenzyme B12 readily accepts a methyl group or hydroxyl methyl group (bound to Co) that can be
transferred to add a carbon to a substrate
•Coenzyme B12 reduces -CH(OH) group to –CH2 group

•Both oxymyoglobin and cytochrome P450 contain dianion of protoporphyrin-IX.
•Oxymyoglobin has fifth ligand bonded to metal centre from protein hackbone but in cytochrome P450
one S-atom of cysteine is coordinated instead of histidine from protein backbone.
•Both contain single active site [Fe (III)]

371
Procaine is a local anesthetic drug of aminoester group. It is used primarily to reduce the pain of
intramuscular injection of penicillin.
Warfarin is used as an anticoagulant. It is commonly used to treat blood clots such as deep vein
thrombosis and pulmonary embolism and to prevent stroke in people who have atrial fibrillation values
heart diseases as artificial heat value.
Cefalexin, also spelled cephalexin, is an antibiotic that can treat a number of bacterial infections. It kills
gram-positive and same gram-negative bacteria by dissrupting the growth of the bacterial cell wall.
Cefalexin is a beta-lactam antibiotic within the class of first-generation cephalosposins.

In oxymyoglobin, Fe+3 present in low spin. Thus, have configuration t2g5 eg0 i.e one unpaired electron.
[Fe(ox)3]3-
Fe+3 = 3d5
(B) [Fe(CN)6]-3
Fe+3 → 3d5
(C) [NiCl4]2-
Ni+2 = d8 = t2g4 eg4
2 unpaired electron
372
(D) [Cu(NH3)4]2+
Cu+2 = t2g5 eg4
1 unpaired electron

(A) Ni present in coenzyme F450 (III) which catalyzes the release of methane (Y) in the final step of
methanogenesis.
(B) Zn present in carbonic anhydrase (I) which catalyses the hydration of CO2 into H2CO3 (Z).
(C) Mo present in Xanthine oxidase (II) which catalyzes the oxidation of Xanthine to uric acid (X).
It is an orally active antitumor agent. Its action seems to be similar to that of Cisplatin, but with the
added feature that its ligands protect it from reaction in digestive system and allow it to be absorbed into
blood stream.
•Glutathione (GHS) is capable of preventing damage to important cellular components caused by
reactive oxygen species.
has promising anticancer activity as it binds to GSH and when followed by oxidation, promotes binding
to guanine in DNA.
shows anti-metastatic action as instead of binding with DNA, it interacts with actin type proteins on cell
surface or with collagens of extra-cellular matrix, which leads to reduced mobility of invasive cancer
cells,

The molecular orbital diagram for binding of O2 to myoglobin is
373
this is responsible for the formation of ϭ bond and the orbitals involved for its formation are π* of O2
and dz2 of Fe(II)

In the catalytic cycle of cytochrome P450, peroxo complex [(porphyrin)FeIII(OOH)] undergoes
protonation which leads to removal of one oxide ion as water via heterolytic O-O cleavage to form
oxyferryl complex with one electron having been oxidized from π -HOMO of porphyrin ring leaving it
as a radical cation i.e. [(porphyrin)+●FeIV(O)]

Zeolite is used for capturing CO2,
Indium tin oxide (ITO) is a form of perovskite used in solar cells.
LiCoO2, Lithium cobalt oxide is a dark blue or bluish-gray crystalline solid, and is commonly used in
the positive electrodes of lithium-ion batteries
Pt alloy is used in fuel cells. Pt is used as the catalyst for both the hydrogen oxidation reaction (HOR)
occurring at the anode and the oxygen reduction reaction (ORR) at the cathode.

Biological function of Hemerythrin and Hemocyanin is O2 transport.
Cytochrome P450 and Tyrosinase are Oxygenase
Rieske Protein and Azurin are used for electron transfer.

In 3-iron ferredoxins, the number of sulfide bridges is 3 and cysteinyl ligands are also 3
374

Rubredoxin consist of Fe+2 centre with Tetrahedral geometry, hence statement (A) is correct.
Reduced form of iron is paramagnetic in nature, statement (B) incorrect.
Due to presence of asymmetric electrons in eg orbitals, Jahn-Teller distortion is observed. Thus
statement (C) is correct.
Rubredoxins are [1Fe–4S] clusters, hence statement (D) is incorrect.

376
Analytical Chemistry
CSIR NOV 2020

1. Correct statement for 'Inductively Coupled Plasma Atomic Emission Spectroscopy' is
(a) It is unsuitable for all non-metals.
(b) Simultaneous determination of only metals is possible.
(c) Induction coil stabilizes plasma.
(d) Oxide formation lowers atomization of metal.
2. Thermometric titration gives best results when

A. ⃒ ΔH⃒ is high
B. ΔG < 0
C. Heat of mixing of titrant with titrant is high
D. Titrant is used as dilute solution
The answer is
1. A and B
2. B and C
3. C and D
4. A and D
CSIR DEC 2019

3. The pair of light source and atomizer resulting highest sensitivity to atomic absorption
spectrometric measurement is:
(1) Hg lamp, nitric oxide flame
(2) Hg lamp, graphite furnace
(3) Hollow cathode lamp, graphite furnace
(4)Hollow cathode lamp; acetylene-nitric oxide flame
4. In spectrofluorimetric determination in solution

A. absorbance of analyte solution is kept near to 0.05
B. oxygen is eradicated from solution
C. pH of solution is controlled
D. wavelength of incident light is always above 400 nm
Correct from the above is
(1)A, B and D
(2)B, C and D
(3)A, B and C
(4)A, C and D
5. Match the items in column I with those of column II

377
Correct match is
(1)a-ii; b-iv, c-i, d-iii
(2)a-iii; b-i; e-ii; d-iv.
(3)a-iii; b-ii; c-iv, d-i
(4)a-i; b-iii; e-iv, d-ii
CSIR JUNE 2019

6. The role of H3PO4 in the estimation of Fe (II) with K2Cr2O7 using diphenylamine sulphonate as
indicator is to
(a) avoid aerial oxidation of Fe(II)
(b) reduce the electrode potential of Fe+3 –Fe+3
(c) stabilize the indicator
(d) stabilize K2Cr2O7
7. Incorrect statement for amperometric titration is

(a) it is based on measurement of diffusion current.
(b) its sensitivity is always higher than those of spectrophotometric titrations
(c) it does not generally require an indicator
(d) it requires inert atmosphere (N2 /Ar)
CSIR DEC-2018
8. Match the items of Column I with those of Column II.
Column-I Column II
(A) Laser source (I) Electron Capture Detector
(B) Thermometric titration (II) Polarography
(C) Gelatin (III) Heat of reaction
(D) Gas-liquid chromatography (IV) Spectrofluorimetry
Correct answer is:
(1) a-iv; b-iii; c-ii; d-i
(2) a-i: b-iii; c-ii; d-iv
(3) a-iv; b-ii; c-iii; d-i
(4) a-iii; b-ii; c-iv; d-i
CSIR JUNE 2018

378
9. Height equivalent to theoretical plate (HETP) in gas liquid chromatography depends

significantly on which of the following?
(A) Temperature of column
(B) Velocity of carrier gas
(C) Packing of column
(D) Column material
Correct answer is
1. A, B and C
2. C and D
3. B, C and D
4. A and C
CSIR DEC 2017

10. To determine the bond parameters at 25°C, electron diffraction is generally unsuitable for
both
(a) O3 and NO2
(b) Sulfur and dry ice
(c) NO2 and sulfur
(d) O3 and dry ice
11. Spectrophotometric monitoring is not suitable to determine the end point of titration of:
1. oxalic acid vs potassium permanganate
2. iron(II) vs 1, 10-phenanthroline
3. cobalt(II) vs eriochrome black T
4. nickel (II) vs dimethylglyoxime
12. The peak area of differential thermal analysis curve is proportional to one or more of the
following
A. mass loss
B. mass of the sample
C. heat of decomposition / phase change
1. A only
2. B only
3. A and C
4. B and C
CSIR JUNE 2017

13. Identify the correct statement(s) for phosphorimetric measurement from the following:
A. It is done after a time delay when fluorescence, if present becomes negligible
B. Immobilization of analyte increases phosphorescence.
C. Phosphorescence decreases in the presence of heavy atoms
1. A only

379
2. A and B
3. A and C
4. Band C
14. Identify correct statements from the following:

A. Area of differential thermal analysis peak is proportional to amount of sample.
B. Area of differential thermogravimetric analysis curve is proportional to mass loss.
C. Phase transition cannot be studied , with differential scanning calorimetry.
D. Simultaneous determination of two metal ions is possible with thermogravimetric analysis.
1. A, B and C
2. A, B and D
3. B, C and D
4. A, C and D
CSIR DEC 2016

15. The primary analytical method (not using a reference) is:
1) inductively coupled plasma emission spectrometry
2) energy dispersive X-ray fluorescence spectrometry
3) anodic stripping voltammetry
4) isotopic dilution mass spectrometry
CSIR JUNE 2016

16. Decomposition temperature of CaCO3 in thermogravimetric analysis will be highest in
dynamic atmosphere of:
1. nitrogen
2. synthesis gas
3. 1:1 mixture of O₂ and CO
4. water gas
CSIR DEC 2015

17. Correct statement for coulometry is
1. it is based on Faraday's law of electrolysis
2. It is a type of voltammetry
3. it is based on Ohm's law
4. it uses ion selective electrode
18. Pick the correct statements about Atomic Absorption Spectrometry (AAS) from the following:
A. Hg lamp is not a suitable source for AAS
B. Graphite furnace is the best atomizer for AAS
C. Non-metals cannot be determined with AAS
D. AAS is better than ICP-AES for simultaneous determination of metal Ions.
Correct answer is:
(a). A, B and C

380
(b). B, C and D
(c). C, D and A
(d). D, A and B
19. The calibration curve in spectrofluorimetric analysis becomes non-linear when

(a). molecular weight of analyte is high
(b). intensity of light source is high
(c). concentration of analyte is high
(d). molar absorptivity of analyte is high
CSIR JUNE 2015

20. Differential pulse polarography (DPP) is more sensitive than D.C. Polarography (DCP).
Consider following reasons for it:
1. Non-faradic current is less in DPP in comparison to DCP
2. Non-faradic current is more in DPP in comparison to DCP
3. Polarogram of DPP is of different shape than that of DCP
Correct reason(s) is/are:
A. 1 and 3
B. 2 and 3
C. 2 only
D. 1 only
21. Considering the following parameters with reference to the fluorescence of a solution:
1. Molar absorptivity of fluorescent molecule
2. Intensity of light source used for excitation
3. Dissolved oxygen
The correct answer for the enhancement of fluorescence with the increase in these parameters
is/are
A. 1 and 2
B. 2 and 3
C. 1 and 3
D. 3 only
CSIR DEC 2014

22. The gas commonly used in generating plasma in Inductively Coupled Plasma Atomic Emission
Spectroscopy (ICPAES) is:
(1) Argon
(2) Carbon dioxide
(3) Nitrous oxide
(4) hydrogen
23. Gel permeantion chromatography can be used to separate which of the following:
(1) Lanthanides

381
(2) Alkaline earths

(3) Fatty acids
(4) Low molecular weight peptides
(1) A and B
(2) B and C
(3) C and D
(4) A and D
CSIR JUNE 2014

24. The use of dynamic inert atmosphere in thermogravimetric analysis (TGA):
(1) decreases decomposition temperature
(2) decrease weight loss
(3) reduces rate of decomposition
(4) increases weight loss
25. The correct statements for hollow cathode lamp (HCL) from the following are:
(A) HCL is suitable for atomic absorption spectroscopy (AAS)
(B) lines emitted from HCL are very narrow
(C) the hardening of lamp makes it unsuitable for AAS
(D) transition elements used in lamps have short life
(1) A, B and C
(2) B, C and D
(3) C, D and A
(4) D, A and B
CSIR DEC 2013

26. In the atomic absorption spectroscopic estimation of Fe(III) using O2 / H2 flame, the
absorbance decreases with the addition of:
(1) CO3+2
(2) SO42-
(3) EDTA
(4) Cl-
CSIR JUNE 2011

27 The FALSE statement for a polarographic measurement procedure is:
(a) O2 is removed
(b) Dropping mercury electrode is working electrode.
(c) Id is proportional to concentration of electro active species.
(d) Residual current is made zero by adding supporting electrolyte
CSIR JUNE 2012

382
28.The spectrophotometric response for the titration of a mixture of Fe+3 and Cu+2 ions against
EDTA is given below.
The correct statment is:

(a) Volume ab = [Fe+3 ] and volume cd= [Cu+2]
(b) Volume ab = [Cu+2] and volume cd = [Fe+3]
(c) Volume ab = [Fe+3] and volume ab = excess EDTA
(d) Volume ab = [Cu+2] and volume cd = excess EDTA

In inductively coupled plasma atomic emission spectroscopy, the plasma gas flows in a helical pattern
(i.e. induction coil) which provides stability and helps to late thermally the outside quartz tube.

In thermometric titration, the determinant of the degree to which a reaction will proceed to completion is
the free energy change, which must be favourable. Other condition to obtain best result in thermometric
titration are
•The reaction should be accompanied by sufficient heat change.
•Heat of dilution should be negligible
•Reaction should be a simple one step changed
•Transfer on heat between the titration vessels and its surrounding should be avoided.

• The hollow cathode lamp is an excellent, having highest sensitivity, bright line source for most
of the elements determinable by atomic absorption.
• The most advanced and widely used high sensitivity sampling technique for atomic absorption is
the graphite furnace. Detection limit for the graphite furnace fall in the ng/L range for most
elements. The sample is atomised in a very short period of time, concentrating the available
atoms in the heated cell and resulting in the observed increased sensitivity.
(a) In spectrofluorimetry the wavelength of incident light can range from 200 nm to 900 nm.
(b) Intensity and colour of the fluorescence of many substance depends upon the pH of solutions.
(c) Since, presence of O2 decreases the fluorescence, thus oxygen is eradicated from the solution.
(d) In flourimetry absorbance of analyte solution is generally kept near to 0.05.

383

• In conductometric titration the end point of titration is determined by means of conductivity
measurements. For example, via conductance/resistance vs volume of alkali plot.
• Amperometric titration refers to a class of titrations in which the equivalence point is determined
through measurement of the electric current produced by the titration reaction.
• Differential pulse polarography is an electrochemical technique where the cell current is
measured as a function of time and as a function the potential between the indicator and reference
electrodes.

H3PO4 is used in the estimation of Fe(II) with K2Cr2O7 using diphenylamine sulphonate as indictor to
reduce the electrode potential for the Fe+3 →Fe+2 reaction by stabilising the ferric ion.

•Copper (Cu), Silver (Ag) and Gold (Au) are called currency metal (present in native form).
Amperometric titration is the one of the economic technique for estimation of these metals.
• It is a class of titration in which the equivalence point is determine through measurement of electric
current produced by the titration reaction.
• Amperometric titration sensitivity is always higher than than those of spectrophotometeric titrations.
•Amperometric titration does not generally require an indicator.
•Amperometric titration does not require inert atmosphere.

Thermometric titration is the method in which a titrant is added stepwise to a vessel containing another
reactant. The enthalpy change on heat of reaction causes a temperature change which when plotted
versus volume of titrant is used to detect the end point.
(i) Electron capture detector is a device for detecting atoms and molecules in a gas and is used in atoms
and molecules in a gas and is used in Gas-liquid chromatography.
(ii) The abnormal peak which appears in polographic titration can be supposed by addition of Gelatin.
(iii)In spectrofluorimetry laser may used as source.

A commonly used measure of the separating efficiency of a column is height equivalent theoretically
plate (HETP). It can be determined by van Deemter equation.
HETP depends upon
• Mean carrier gas velocity
• Temperature of the column
• Packing of the column
HETP does not depends upon particle size

Electron diffraction is used to get the bond parameters of gaseous samples

384

(a) Oxalic acid versus potassium permanganate:
End-point is colorless → pink purple (λmax = 525 nm)
(b) Iron (II) versus 1, 10-phenanthroline:
End-point is colorless → Reddish-orange (λmax =512 nm)
(d) Nickel (II) versus Dimethylglyoxime:
End-point is colorless Red (λmax = 445 nm)
(c) Cobalt (II) versus Eriochrome Black-T:
End-point is Blue-green → green
(pH=8) (λmax =660 nm) (λmax =600 nm)
Free EBT → Co(II) + EBT complex
Since, color change at end-point is not significant for option(c) which is requirement of the
spectrophotometric titration. Therefore, color monitoring method is not suitable in this case.

The peak area of differential thermal analysis is proportional to
(i)mass of the sample
(ii) heat of decompositional phase change

Phosphorescence has been observed form a wide variety of compounds and is differentiated from
fluorescence by long lived emission of light after extinction of the excitation source i.e. it done after
fluorescence, if parsists.
Phosphorescence increases when heavy atoms like iodine silver and lead etc. are added.
Phosphorescence increases, when analyte used become immobile.
Hence, both (A) and (B) are correct.
Correct statement are
•Area of different thermal analysis peak is proportional to amount of sample
•In the thermo gravimetric analysis area of curve is proportional to mass loss
•In thermo gravimetric analysis two metal ion simultaneously determine.

Primary analytical method is isotopic dilution mass spectrometry (not using a reference).

Decomposition temperature of CaCO3 in thermogravimetric analysis will be highest in dynamic
atomosphere due to the presence of 1:1 mixture of O2 and CO.

Coulometry is based on Faraday's law of electrolysis

385
Inductively coupled plasma atomic spectroscopy (ICP-AES) is an analytic technique used for detection
for trace metals and it is better than AAS for simultaneous determination of metal ions. Hence, option
(d) is correct.
In Atomic Absorption Spectroscopy mercury lamp is not suitable source but hollow cathode lamp (HCI)
are the most common radiation source in Atomic Absorption Spectroscopy and atomizers most
commonly used are flame and electro thermal (graphite). Solid sample is used in determination.

Thermometric titration is the method in which a titrant is added stepwise to a vessel containing another
reactant. The enthalpy change on heat of reaction causes a temperature change which when plotted
versus volume of titrant is used to detect the end point.
(1) Electron capture detector is a device for detecting atoms and molecules in a gas and is used in atoms
and molecules in a gas and is used in Gas-liquid chromatography.
(2) The abnormal peak which appears in polographic titration can be supposed by addition of Gelatin.
(3)In spectrofluorimetry laser may used as source
The residual current in case of DCP is non-faradic current which should be minimum to get the accurate
result. This problem of non-faradic current is overcome by use of DPP in which non-faradic current is
less than DCP. That is why DPP is more sensitive than DCP.
Though the polarograph is different in both cases but it has nothing to do with sensitivity.

Increase of intensity of light used increases fluorescence as the fluorescence life-time increases. Molar
absorptivity increases absorbance which further enhances fluorescence.
22. Correct answer (a)

For ICP-OES and ICP_MS argon is most suitable gas to generate plasma.
A number of gases cane be used to produce plasma, like Ar, Ne, N2, O2, H2 , air and mixture of gases.
The physical properties of the gases play a decisive role in this regard. Such important properties are
ionization and dissociation energy, thermal conductivity, atomic weight and chemical reactivity.
Argon belongs to the group of inert gases. It means that it does not react with the material during
production of plasma. Its atomic weight - the highest among all plasma gases and it generates high
kinetic energy of the plasma beam. Due to its low ionization potential argon is excellently suitable for
generating the plasma beam. However, argon has a low thermal conductivity and a low thermal capacity
which limits its application is some specific areas only.

Gel permeation chromatography is a size exclusion chromatography , that separates analytes on the
basis of size. So, the size difference in fatty acids and low molecular weight peptides is greater so they
can be separated by using gel permeation chromatography.

386
In thermogravimetric analysis (TGA) use of dynamic innert atmosphere is decrease with respect to
temperature.

Statements A, B and C are correct.

Chemical reactions between analyte and matrix that prevent the atomization of the analyte. One
common one is that Sulfate or phosphates anions will form non-volatile salts with Fe+3 , so its signal
decreases. Can be treated in two ways
1. Releasing agents can add to metal to prevent formation of interference complexes. example EDTA or
8-hydroxyquinoline.

(a) O2 must be removed as it give its own polarogram, due to following reactions,
O2 + 2H+ + 2e- = H2O ; O2 + 4H+ + 4e- → 2H2O
(b) Dropping mercury electrode is the working electrode
(c) Id ∝ C
(d) Residual current need not to be made zero.

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1

1. Ni(CN4)2- and Ni(Cl4)2- complex ions are :

3. The term symbol of a molecule with electronic configuration:

4. Consider two redox pairs:

(a) HOMO/LUMO are ϭ* and ϭ* respectively.

6. The correct order of LMCT energies is: [CSIR-JUNE 2011]

7. For the complexes

(a) (A) and (D)

8. The possible J values for 3D term symbol are [CSIR-JUNE 2011]

9. Which of the following compound show a charge-transfer band? [CSIR-JUNE 2011]

15. Observe the following electronic transition of a diatomic molecule.

The allowed transitions are [CSIR-DEC 2011]

(a) (A) and (C) only

19. For the following outer sphere electron transfer reactions.

20.The coordination number and geometry of cerium in [Ce(NO3)6] -2 are respectively,

21. As a ligand Cl- is: [CSIR-JUNE 2012]

22. The correct d-electron configuration showing spin-orbit coupling is

23. The nucleophilic attack on olefins under mild conditions:

(d) Requires activation by coordination to metal.

25.The number of microstates for d5 electron configuration is: [CSIR-JUNE 2012]

27 In [Mo2(S2)6]-2, cluster the number of bridging 𝐒𝟐$𝟐 and coordination number of Mo

29. The number of possible isomers of [Ru(PPh3)2 (acac)2](acac = acetylacetonate) is:

31. The electric dipole allowed transition in a d² atomic system is

34. The correct spinel structure of Co3O4 is:

38. The reaction of Pt(NH3)42- with two equivalents of NH3 produces

Identify the correct statement about them

47. The ∆t of the following complexes

51. MnCr2O4 is likely to have a normal spinel structure because

(b) d x2-y2 and dz²

53. The most appropriate structure for the complex [Pt2(NH3)2(NCS)2(PPh3)2] is

54. In bis(dimethylglyoximato)nickel(II), the number of Ni-N, Ni-O and intramolecular hydrogen

60. Reaction of [Ru(NH3)5(isonicotinamide)]+3 with [Cr(H2O)6] +3 occurs by inner sphere

[Fe(phen) 3] +3 /[Fe(phen) 3] +3 3.0 x107 M-1

66. In the following reaction [PtCl4]-2 +NO2-, is →A + NH3 →B , compound B is

67. The number of stereoisomers of trans-[CoCl2(triethylenetetraamine)]Br is

The correct answer is

69.Base hydrolysis of [CoCl(NH3)5] +2 is an overall second order reaction, whereas that of

(A) Presence of ionizable proton in [CoCl(NH3) 5] +2 but not in [Co(CN) 6]-3,

72. The three dimensional structure of compound [Co(Co(NH3)4(OH)2)3]Br6 , has

75. The electric-dipole allowed transition among the following is

83. The correct statement for Mn-O bond lengths in [Mn(H2O)6 ] 2+ , is

(d) its rate is dependent only on the concentration of [OH] -

89. Choose the correct statements about Tanabe-Sugano diagrams

92. The symmetry-allowed atomic transition among the following is

94. The number of microstates present in 3F-term is [CSIR-JUNE 2016]

95. Chelate effect is [CSIR-JUNE 2016]

97. The first excited state of hydrogen molecule is [CSIR-JUNE 2016]

98. Complex [Cr(bipyridyl)3]+3 , shows red phosphorescence due to transition

104. The nephelauxetic parameter β is highest for [CSIR-DEC 2016]

106. For [Ce(NO3)4(OPPh3)2] from the following

107. Consider the following statements for [FeO4]-4

Correct match of entries given in two columns is [CSIR-JUNE 2017]

118. Match the items in the three columns.

The correct answer is [CSIR-JUNE 2017]

D. [CoF6]-3 [CSIR-DEC 2017]

125. Mismatch among the following is [CSIR-DEC 2017]

130. Consider the following statements:

131. Consider the statements A - D regarding equation I-III:

132. The allowed electronic transition in fluorine molecule is [CSIR-JUNE 2018]

134. The intermediate [Fe(SCN)(H2O)5]+2 is detected in the reaction of [Co(NCS)(NH3)5]+2 with

139. Consider the two sets of molecules.

140. Self-exchange electron transfer is fastest in [CSIR-JUNE 2019]

141. Consider the following reaction: