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1711735503046Inorganic Chemistry PYQ eBook 2024 Edition
1711735503046Inorganic Chemistry PYQ eBook 2024 Edition
1711735503046Inorganic Chemistry PYQ eBook 2024 Edition
Coordination Chemistry 1
Organometallic Compounds 94
Main Group Elements 214
Nuclear Chemistry 279
Inorganic Spectroscopy 290
Lanthanides & Actinides 323
Chemical Bonding 348
Bioinorganic Chemistry 385
Analytical Chemistry 426
1
Coordination Chemistry
2
Coordination Chemistry
2. According to Crystal Field Theory, Ni2+ can have two unpaired electrons in
(a) 1∑+g
(b) 3∑-g
(c) 1∑ - g
(d) 3∑ g+
5. The complex [Mn(H2O)6]+2 has very light pink colour. The best reason for it is
10. Cis and trans complexes of the type [PtA²X²] are distinguished by
]
(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
4
Coordination Chemistry
12. The term symbol for the ground state of nitrogen atoms is
(a) 3P0
(b) 4P3/2
(c) 1P1
(d) 4S3/2
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
(a) Square planar and one
(b) Tetrahedral and one
(c) Square planar and two
(d) Tetrahedral and two
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:
18. The correct order of d-orbital splitting in a trigonal bipyramidal geometry is:
24. The number of spin-allowed ligand field transitions for octahedral Ni(II) complexes with 3A2g,
ground state is:
(a) Two
(b) Three
(c) One
(d) Four
26. The set of allowed electronic transitions among the following is:
28. The light pink color of [Co(H2O)6] +2and the deep blue color of [CoCl4]-2 are due to
(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.
(a) 2
(b) 3
(c) 4
(d) 5
30. The total number of Cu-O bonds present in the crystalline copper(II) acetate monohydrate is:
(a) 10
(b) 6
(c) 8
(d) 4
(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:
(a) 2
(b) 4
(c) 6
(d) 8
33. In the solid state, the CuCl5 ion has two types of bonds. These are
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:
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
(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
39.The electronic transition responsible for the colour of the transition metal ions is
(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
(a) T2g + Eg
9
Coordination Chemistry
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)
(a) A and B
(b) B and C
(c) C and D
(d) A and D
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,
43.Intense band at 15000 cm-1 in the UV-visible spectrum of [Bu4N]2 Re2 Cl8 is due to the
transition
(a) π→π*
(b) δ→ δ*
(c) δ → π*
(d) π→ δ*
44. Identify the order representing increasing π -acidity of the following ligands C2F4, NEt3, CO
and C2H4
45. The species with highest magnetic moment (spin only value) is
(a) VCl64-
(b) (η5-C5H5)2 Cr
(c) [Co(NO2) 6] 3-
(d) [Ni(EDTA)] 2-
10
Coordination Chemistry
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
(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
49. For an electronic configuration of two non-equivalent π electronics [π1, π1] which of the
following terms is not possible?
(a) 1Σ
(b) 3Σ
(c) 3Δ
(d) 3𝛟
50. Among the following, the correct combination of complex and its color is
Complex Colour
(a) [Co(CN4)]2- Red
(b) [Co(Cl4)]2- Orange
11
Coordination Chemistry
(a) Mn2+ 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 one of the 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
(a)
(b)
(c)
(d)
12
Coordination Chemistry
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
56. If L is a neutral mono-dentate ligand, the species, [AgL4]2+ , [AgL6]2+ and [AgL4] 3+
respectively are
57. [CoL6] 3+ is red in colour whereas [CoL׳6] 3+ is green. L. and L' respectively corresponds to,
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
59. The term symbol that is NOT allowed for the np2 configuration is
(a) 1D
(b) 3P
(c) 1S
(d) 3D
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
(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.
(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
(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
14
Coordination Chemistry
(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
(a) trans-[PtCl2(NO2)(NH3)]-
(b) cis-[PtCl(NO2)(NH3)] -
(c) trans-[PtCl2(NH3)2]
(d) cis-[PtCl3(NO2)2] -2
(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
(A) Presence of 6A1g ground state
(B) Disallowed transition by spin selection rule
(C) Presence of 2T2g ground state
(D) Charge transfer transition
70. The configuration [Ne] 2p1 3p1 has a 3D term. Its levels are
71. The spin-only magnetic moment and the spectroscopic ground state term symbol of manganese
center in [MnF6] -3 ion respectively, are
73. The spin-only and spin plus orbital magnetic moments of [CrCl6]-3 are
74. In transition metal phosphine (M-PR3) complexes, the back-bonding involves donation of
electrons from
(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
(a) ³P1
(b) 1P1
(c) 3P2
(d) 3P0
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:
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
(a) A, B and C
(b) B, C and D
(c) A and D
(d) B and C
17
Coordination Chemistry
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
80. The term symbol for the first excited state of Be with the electronic configuration 1s2 2s1 3s1 is.
(a) 3S1
(b) 3S0
(c) 1S0
(d) 2S1/2
81. The oxidizing power of [CrO4]2- , [MnO4]2- and [FeO4]2- follows the order
82. Using crystal field theory, identify from the following complex ions that shows same μeff (spin
only) values
(A) [CoF6] 3-
(B) [IrCl6] 3-
(C) [Fe(H2O) 6] 2+
(a) A and B
(b) B and C
(c) A and C
(d) A, B and C
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)
85. The formation constant for the complexation of M+ (M= Li, Na, K and Cs) with cryptand,
C222 follows the order
86. [MnO4] - is deep purple in colour whereas [ReO4] - is colourless. This is due to
greater energy required for
87. The correct statement about the substitution reaction of [Co(CN) 5Cl] 3- with OH- to give
[Co(CN)5(OH)] 3- is,
88. Aqueous Cr+2 effects one electron reduction of [Co(NH3)5Cl] +2 giving compound Y. Compound
Y undergoes rapid hydrolysis. Y is,
(a) [Co(NH3)5]+2
(b) [Co(NH3)5(OH) ]+
(c) [Co(NH3)4(OH)2]
(d) [Cr(H2O)5Cl]+2
(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
91. Possible term symbol(s) of the excited states of Na atom with the electronic configuration [1s2
2s2 2p6 3p1] is/are
(a) 2S1/2
(b) 2P3/2 and 2P1/2
(c) 1S0 and 1P1
(d) 3P0 and 3P1
(a) 3F→ 1D
(b) 3F→ ³D
(c) 3F→ 1P
(d) ³F→ ³P
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
99. The complex that shows orbital contribution to the magnetic moment, is
(A) [Cu(H2O)6]+2
(B) [Ni(H2O)6]+2
(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-
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:
𝝀𝜶
(A) μeff = μs )𝟏 − 𝚫 ,
(B) μeff = -𝒏(𝒏 + 𝟐)
(c) μeff =-𝟒𝒔(𝒔 + 𝟏) + 𝑳(𝑳 + 𝟏)
21
Coordination Chemistry
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
(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
(a) NO2-
(b) NCS-
(c) Cl-
(d) OH-
105. The 2Eg ←4A2g transition in the electronic spectrum of [Cr(NH3)6]+3 occurs nearly at
(a) 650 nm
(b) 450 nm
(c) 350 nm
(d) 200 nm
A. It is paramagnetic
B. It has Td symmetry
C. Adopts distorted square planar geometry
D. Shows approximately D2d symmetry
The correct answer is
(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
(a) 2H , 4F and 2D
(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
(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
(a) 3.16x106
(b) 2.0x106
(c) 6.32x106
(d) 3.16x106
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
23
Coordination Chemistry
(a) 1π
(b) 3∑
(c) 1∆
(d) 1∑
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:
(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
Correct match of entries given in two columns is
(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
(a) 1.73
(b) 1.81
(c) 1.63
(d) 1.93
24
Coordination Chemistry
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
(a) A, B, and C
(b) A, C, and D
(c) B, C, and D
(d) B and D
119. For the following complexes, the increasing order of magnetic moment (spin only value) is
A. [TiF6]-3
B. [CrF6]-3
C. [MnF6]-3
D. [CoF6]-3
(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:
(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)
25
Coordination Chemistry
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
(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)
(c)
26
Coordination Chemistry
(d)
123. For high spin and low spin d6 octahedral complexes (ML6), the generally observed spin
allowed transitions respectively, are
(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
(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
126. The total degeneracy of the ground term of Co11 (high spin) in octahedral geometry is
1. 18
2. 12
3. 28
4.9
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
(a) Co+2
(b) Ni+2
(c) Cu+2
(d) Co+2
27
Coordination Chemistry
128. For electronic spectra of K2CrO4 (A) and K2MoO4 (B) the correct combination is
129. The lowest energy state of a 1s1 2s1 electronic configuration, according to hund's rule, is
(a) 3S0
(b) 1S0
(c) 3S1
(d) 1S1
(b) ∑&
𝒈 → ∑𝒈
&
&
(c) ∑𝒈 → πu
28
Coordination Chemistry
(d) ∑&
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
(a) 4 and I2-
(b) 4 and I2
(c) 3 and VO+2 , Cu+2
(d) 3 and NO, Cu+2
135. For magnesium complex of EDTA2- , the number of N-donor and O-donor centers, are
respectively.
(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
(a) t62g e1g , t32g e1g , t62g e3g
(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
(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]
138. The isomers A and B undergo base hydrolysis by forming a trigonal bipyramidal
intermediate.
The correct statement is
29
Coordination Chemistry
(a) F<Cl< Br
(b) Br<Cl< F
(c) Cl< Br< F
(d) Br< F<Cl
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 .
The correct statements are
(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
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
(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
(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
31
Coordination Chemistry
149. FeCr2O4 and NiGa2O4 have normal and inverse spinel structures, respectively. The correct
statement is
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)
(a)4.89 BM for both A and B
(b)0 BM for both A and B
(c) 4.89 BM for A and 0 BM for B
(d) 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
(a)Two ligand→ metal (ϭ → t2g and ϭ →a1g*)
(b)One ligand →metal (ϭ →eg)
(c)Two ligand→ metal (ϭ →t2g and ϭ →eg )
(d)One ligand→ metal (ϭ →t2g)
[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
(a) (a) only
(b) (b) only
(c) (a) and (b) only
(d) (b) and (c) only
155. The pair of compounds in which both members show LMCT band in their electronic spectra
is
(a) [FeCl4]-2 and [Fe(bpy)3]+2
(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
(a) 4F1/2
(b) 4F3/2
(c) 4F7/2
(d) 4F9/2
158. The number of expected electronic transitions in [Cr(en)3]+3 and trans-[Cr(en)2F]+ at 4 K is,
respectively (en = ethylenediamine)
a. 3 and 3
b. 3 and 4
c. 3 and 5
d. 3 and 6
160. In the following sequence of reactions the correct P, Q and R are respectively
161. The term symbol for the ground state of dinitrogen cation radical
(N2)+ is
(a) 2πu
(b) 2∑"𝒖
(c) 2πg
(d) 2∑&𝒈
(b) 1 and 3
(c) 1, 3 and 4
(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
(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
(a) 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+
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
(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
(a) 𝟒𝑭; 𝟒𝑻𝟏𝒈(𝑭) → 𝟒𝑻𝟐𝒈𝒂𝒏𝒅 𝟒𝑻𝟏𝒈→ 𝟒𝑨𝟐𝒈
(b) 𝟒𝑭; 𝟒𝑨𝟐𝒈→ 𝟒𝑻𝟐𝒈 𝒂𝒏𝒅 𝟒𝑨𝟐𝒈→ 𝟒𝑻𝟏𝒈(𝑭)
(c) 𝟐𝑮; 𝟐𝑬𝒈→𝟐𝑻𝟏𝒈 𝒂𝒏𝒅 𝟐𝑬𝒈→ 𝟐𝑻𝟏𝒈
(d) 𝟐𝑭; 𝟐𝑨𝟐𝒈 → 𝟐𝑻𝟐𝒈𝒂𝒏𝒅 𝟐𝑨𝟐𝒈→ 𝟐𝑻1𝒈(𝑭)
35
Coordination Chemistry
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
(b) 𝑫𝟑𝒅 ; 𝒅𝒛𝟐 > 𝒅𝒙𝒚 , 𝒅𝒙𝟐−𝒚𝟐 > 𝒅𝒙𝒛, 𝒅𝒚𝒛
(c) 𝑫𝟑𝒅 ; 𝒅𝒙𝟐−𝒚𝟐 > 𝒅𝒛𝟐 , 𝒅𝒙𝒚 > 𝒅𝒙𝒛, 𝒅𝒚𝒛
(d) 𝑫𝟑𝒉 ; 𝒅𝒛𝟐> 𝒅𝒙𝟐−𝒚𝟐 , 𝒅𝒙𝒚 > 𝒅𝒙𝒛, 𝒅𝒚𝒛
170. An octahedral d6 complex has a single spin-allowed absorption band. The spin-only magnetic
moment (B.M.) and the electronic transition for this complex, respectively, are
(a) 0 and 1T1g¬1A1g
(b) 4.9 and 5T2g¬5Eg
(c) 4.9 and 5Eg¬5T2g
(d) 0 and 1T2g¬1A1g
171. The Second order rate constants for the outer sphere self-exchange electron transfer
reactions for [Ru(NH3)6]2+/[Ru(NH3)6]3+ and [Co(NH3)6]2+ / [Co(NH3)6]3+ are 9.2x102 M-1Sec-1 and £
10-9 M-1 Sec-1 , respectively. The Correct rationale for the above data is:
(a) The change in the number of σ* -electrons in Co(II)/Co(III) system.
(b) The change in the number of p*-electrons in Co(II)/Co(III) system.
(c) The change in the number of both σ* and p* – Co(II)/Co(III)system.
(d) The change in the number of σ*-electrons in Ru(II)/Ru(III) system.
173. The electronic spectrum of an aqueous solution of [Ni(H2O)6]2+ shows three distinct bands: A
(~ 400nm), B(~ 690nm) and C(~ 1070nm). The transitions assigned to A, B and C , respectively,
are
(a) T1g(P) ¬ A2g, T2g¬ A2g, and T1g¬A2g
(b) T1g(P) ¬ A2g, T1g¬ A2g, and T2g¬ A2g
(c) T2g¬ A2g, T1g¬ A2g, and T1g (P) ¬ A2g
(d) T1g¬ A2g, T2g¬ A2g, and T1g (P)¬ A2g
36
Coordination Chemistry
174. In the following electron transfer reactions, the one in which the bridging ligand comes from
the reductant is
(a) [IrCl6]2– + [Cr(OH2)6]2+® Products
(b) [Co(NH3)5Cl]2+ + [Cr(OH2)6]2+® Products
(c) [Fe(CN)6]4– + [IrCl6]2–® Products
(d) [CrO4]2– + [Fe(CN)6]4–® Products
175. Hydrolysis of the purple isomer of the complex [Co(tren)(NH3)Cl]2+ [tren = Tris(2-
aminoethyl) amine] under basic conditions results in two products. The geometry of the
intermediate involved in this reaction is
(a) Trigonal bipyramidal
(b) Square pyramidal
(c) Pentagonal planar
(d) Tetrahedral
176. The coordination numbers of cobalt ion in solid Cs3CoCl5 and zinc ion in solid (NH4)3ZnCl5
are, respectively,
(a) 5 and 4
(b) 4 and 4
(c) 4 and 5
(d) 5 and 5
177. The correct set of possible term symbols for the electronic configuration 1s22s12p1 is
(a) 1P1, 3P2, 3P0, 3S0 (b) 1P0, 3P2, 3P0, 3P1 (d) 1P1, 3P2, 3P0, 3P1
178. The ground state term and the calculated magnetic moment (in BM) for Dy3+ ion respectively,
are
179. Consider four non-interacting 4He atoms, each of which can occupy three energy levels of
energies 0, a and 2a. The number of microstates having total energy E = 3a is
(a) 4
(b) 12
(c) 2
(d) 1
A. An outer-sphere mechanism involves electron transfer from reductant to oxidant, with the
coordination shells or spheres of each staying intact.
B. In inner-sphere mechanism, the reductant and oxidant share a ligand in their inner or primary
coordination sphere which assists in electron being transferred.
181. A yellow-colored complex P upon addition of aqueous HNO3 forms a very pale violet-colored
complex Q. Complex Q on reaction with NaCl forms a yellow-colored complex R. The species P, Q
and R. respectively, that are consistent with the above observation are
182. Given the special transitions for [CrF6]3- complex as, 671 nm [4𝑨𝟐𝒈 ® 4𝑻𝟐𝒈 ], 441 nm [4𝑨𝟐𝒈 ®
4
𝑻𝟏𝒈 (F)] and 291 nm [4𝑨𝟐𝒈 ® 4𝑻𝟏𝒈 (P)], the Racah parameter B¢ is closet to
183. The option showing the correct match for the reactants in Column I with second-order rate
constants (I mol-1 s-1) in Column II for the outer sphere reactions in water at 25oC
38
Coordination Chemistry
184. The option showing the correct match of metal complexes in Column I with the
corresponding Δo (cm-1) values in Column II is
(a) 𝑨 → 𝑸, 𝑩 → 𝑷, 𝑪 → 𝑺, 𝑫 → 𝑹
(b) 𝑨 → 𝑹, 𝑩 → 𝑺, 𝑪 → 𝑷, 𝑫 → 𝑸
(c) 𝑨 → 𝑸, 𝑩 → 𝑷, 𝑪 → 𝑹, 𝑫 → 𝑺
(d) 𝑨 → 𝑷, 𝑩 → 𝑺, 𝑪 → 𝑹, 𝑫 → 𝑸
185. The correct plot of logK vs x (K = stepwise stability constant) for the complex [Al(OH2)6-xFx](3-
x)+
(x=1-6) is
39
Coordination Chemistry
(a) A
(b) B
(c) C
(d) D
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 170 C
11 B 51 D 91 B 131 D 171 A
12 D 52 B 92 B 132 C 172 A
13 C 53 C 93 D 133 B 173 C
14 B 54 A 94 B 134 C 174 D
15 B 55 A 95 B 135 A 175 A
16 B 56 A 96 B 136 A 176 B
17 B 57 A 97 D 137 A 177 D
18 D 58 A 98 C 138 C 178 B
40
Coordination Chemistry
19 C 59 D 99 C 139 B 179 C
20 D 60 A 100 D 140 A 180 B
21 C 61 A 101 A 141 A 181 A
22 C 62 A 102 A 142 C 182 C
23 D 63 C 103 A 143 C 183 A
24 B 64 A 104 D 144 B 184 A
25 C 65 D 105 A 145 C 185 A
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
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.
41
Coordination Chemistry
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.
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
5) d
For a d5 octahedral complex [Mn(H2O)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 is 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
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
11) b
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
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
44
Coordination Chemistry
17) b
Substitution nucleophilic unimolecular conjugate base mechanism.
[CoCl(NH3)5] +2 + OH- →[Co(NH3)4(NH2)Cl] +1 +H2O
,-./ ,123
[Co(NH3)4(NH2)Cl] +1 \⎯⎯⎯⎯⎯⎯^ [Co(NH3) 4(NH2)] +2 + Cl-1
18) d
Explanation
45
Coordination Chemistry
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
24) b
For Ni+2 ion in free state, 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.
46
Coordination Chemistry
Three electronic transitions are 3T2g← 3A2g , 3T1g ←3A2g , 3T1g (P) ←3A2g
25) c
4!
We know that number of microstates= 6!(4"6)!
For d5, r= 5, l=2 Therefore,
n = 2(2l+1)= 2(2x2+1) = 10
9:!
Number of microstates = ;!×;!
= 252 = 7 × 6=
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 .
27) a
[Mo2(S₂)6]-2
The structure of [Mo2(S₂)6]-2 cluster is:
28) c
[Co(H2O)6]+2 → t52g e2g
29) b
30) a
48
Coordination Chemistry
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
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 𝑑> "
orbital
=
Electronic Configuration, 𝑑?> =
= 𝑑@> =
< 𝑑?@ , =𝑑?=" "@ " <𝑑>="
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]
The precursor of this complex is [PtCl4]-2
36) b
Explanation
49
Coordination Chemistry
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
The electronic transition responsible for the colour of the transition metal ions is dπ →dϭ* which is in
according to LFT.
50
Coordination Chemistry
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
51
Coordination Chemistry
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
52
Coordination Chemistry
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+
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
54
Coordination Chemistry
NiBr2 reacts with (Et)(Ph2)P at -78°C in CS2 gives red compound '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)
55
Coordination Chemistry
59) d
For np2 configurations (microstates)
The configuration (IV) violets the Pauli's Principle, Hence term symbol 3D is not possible.
60) a
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
5 0
π* ϭ* π*6e0g
56
Coordination Chemistry
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
57
Coordination Chemistry
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
67) c
68) a
Explanation
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
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
59
Coordination Chemistry
L=2→D
Ground state term symbol ³D
72) a
It is first inorganic optically active compound discovered by Werner.
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
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*).
60
Coordination Chemistry
So, in transition metal phosphine (M-PR3) complexes, the back bonding involves donation of electrons
from M(t2g )→ PR3(σ*)
75) b
For allowed transition : a)Spin multiplicity should be same or ΔS = 0
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.
61
Coordination Chemistry
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
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
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
63
Coordination Chemistry
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
3- 6 4 2
(A) [CoF6] → d (high spin) = t 2g e g 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
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
64
Coordination Chemistry
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
65
Coordination Chemistry
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.
66
Coordination Chemistry
ground state= 4F
First excited state = 4P
4
A2g →4T2g (Δ0)
91) b
For [1s22s2p6 3p1]
9
2s+1=2 × = + 1 = 2
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
67
Coordination Chemistry
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
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
68
Coordination Chemistry
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 ꞵ is for F-
69
Coordination Chemistry
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
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
ABCD AEFG
[Co(NH3)4(NH2)Cl] +1 \⎯⎯⎯⎯⎯^ [Co(NH3) 4(NH2)] +2 + Cl-1
110) b
𝑘(12) = -𝑘(11)𝐾𝑘(22)𝑓 = √5 × 4 × 10H × 2 × 10I × 1.0 = 20× 10; = 2.0× 10J
70
Coordination Chemistry
111) a
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
KL
μeff = μs )1 − M ,
71
Coordination Chemistry
9 9 9:#$
Δ = K = J=; × 10"N cm = J=; cm-1
For Cu+2 → Term is 2D , hence, α = 2 , λ =-625 cm-1
=×("J=;) ×J=; =×J=; ×J=;
μeff = 1.73 )1 − 9:$
, = 1.73 )1 + 9:$
,
=×J=; ×J=;
1.73 )1 + 9:$
, = 1.73{1+ 0.078} = 1.73{1.078} = 1.864
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
72
Coordination Chemistry
(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
+
121) a
Mechanism of base hydrolysis can be given as
[CoCl(NH3)5] +2 + OH- →[Co(NH3)4(NH2)Cl] +1 +H2O
,-./ ,123
[Co(NH3)4(NH2)Cl] +1 \⎯⎯⎯⎯⎯⎯^ [Co(NH3) 4(NH2)] +2 + Cl-1
[Co(NH3) 4(NH2)] +2 +OH- → [Co(NH3)5OH] +2
122) a
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 .
74
Coordination Chemistry
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
In I3 there is interaction between ϭ* antibonding of I2 and non-bonding electron of I-. In case of
-
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+3 (high spin) → 3d7 4s0
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
75
Coordination Chemistry
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
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-
76
Coordination Chemistry
(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] + [Co(CN)5]-3 → [(NC)5Fe-CN-Co(CN)5]-6
-3
electron transfer
\⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯^ [Fe(CN)6]-4 + [Co(CN)5(OH2)]-2
(Inner sphere mechanism)
(II) [Co(bipy)3] + [Co(bipy)3] → [Co(bipy)3]+3 +[Co(bipy)3]+2
+2 +3
132) c
For allowed transition : a)Spin multiplicity should be same or ΔS = 0
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
77
Coordination Chemistry
NO, I2- , Cu+2 and VO+2 is paramagnetic. Hence, EPR active where as I2 is diamagnetic and EPR
inactive.
134) c
- H2O electron transfer
[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]+2 +H2O → [Fe(H2O)6]+3 +SCN-
Intermediate
135) a
136) a
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
78
Coordination Chemistry
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]
(π*)6(ϭ*)0 (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] +[Fe(H2O)6]+3 → [Fe(H2O)6]+3 + [Fe(H2O)6]+2 [Reaction is fast]
+2
(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] → t2g3 eg2 : High spin complex
+2
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
79
Coordination Chemistry
No unpaired electron.
Therefore, it is diamagnetic in nature.
143) c
Ti →d complex: t2g1 eg0
+3 1
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-
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
80
Coordination Chemistry
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-
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-
81
Coordination Chemistry
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
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.
"
μ = "-𝑛(𝑛 + 2) = "-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 = "-𝑛(𝑛 + 2) = "-0(0 + 2) = 0 BM
82
Coordination Chemistry
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.
152) c
+2
[*Co(NH3)6] + [Co(NH3)6]+3 → [*Co(NH3)6]+3 + [Co(NH3)6]+2
High spin low spin
5 2
t2g eg t2g 6 eg0
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:
E=^ to t2g
*Co+2 (t2g5 eg2) → (t2g6 eg1) \⎯⎯⎯⎯^ (t2g5 eg1) → (t2g6 eg0) *Co+3
(electronic transition)
83
Coordination Chemistry
E=^ 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
d3-electronic configuration:
157) c
- H2O electron transfer
[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+
84
Coordination Chemistry
158) d
+3
In [Cr(en)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.
160) b
Solid Thiourea
KNO2 in dil . AcOH \⎯⎯⎯⎯⎯⎯⎯⎯^ N2 gas ↑ + SCN- + H2O
(P) ↓ dil FeCl3
[Hg(SCN)4] 2-
}⎯⎯⎯⎯⎯⎯⎯⎯~ [Fe(H2O)5(SCN)]2+
ef-g12d HgCl2
solution
Colourless (R) Blood red (Q)
161) d
N2+ = ϭ21s ϭ21s* ϭ22s ϭ22s* π22px = π22py ϭ12pz
ϭ12pz = gerade
Ʌ = 0 i.e. Σ
85
Coordination Chemistry
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 = ∑m
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.
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.
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
µ = -𝑛(𝑛 + 2)
= -4(4 + 2) = -4(6) = √24
µ = 4.9 B.M
also, S = 4/2 = 2
spin multiplicity = 2s + 1
=2´2+1
=5
The given system is Ni+2 which is d8 Oh system, hence according to Orgel Diagram
Max wavelength = 1070 nm (corresponds to least energy gap)
A2g® T2g 1070 nm (C)
A2g® T1g 690 nm (B)
A2g® T1g(P) 400 nm (A)
In option (b)
[Co(NH3)5Cl]+2 + [Cr(H2O)6]+2
CO+3(l.s) Cr+2 (H.S)
Since electron transfer takes place from Reductant to oxidant, and reductant cannot form
bridging (here Cl will form bridging and it is with oxidant) hence it is incorrect option.
In option (a)
[IrCl6]–2 + [Cr(OH2)6]+2 [Cl5Ir—Cl— Cr(OH2)5] [IrCl6]–3 + [Cr(OH2)6]+3
91
Coordination Chemistry
During electron transfer, Cl forms bridging and then it is retained with Ir complex, hence this is
just electron transfer reaction and not ligand transfer.
Option (d) undergoes electron transfer as well as ligand transfer by formation of bridging through O
atom
S = |S1+ S2|––––|S1–S2|
9 9 9 9
‘= + =‘ –––– ‘= − =‘
S = 1, 0
S = 2S + 1 = 3, 1
L = |L1 + L2| ––– |L1 – L2| = |0 + 1| ––– |0 -1|
L=1
J = |L + S| ––– |L – S|
If S = 1, |1 + 1| ––– |–1|
S = 2, 1, 0
If S = 0, |1 + 0| ––– |1 – 0| = 1
3
P2 , 3 P1 , 3 P0 , 1 P1
L=5 ® 0®S
S = 5/2 1® P
2®D
3®F
4®F
5®H
9;
J = L + S = 5 + 5/2 = =
6
H15/2
µ = 9 = -𝐽(𝐽 + 1)
9&s(s&9)&t(t&9)"o(o&9)
9= =t(t&9)
[putting all values]
µeffective = 10.65
Generally, step-wise stability constant value decreases with successive replacement by the ligand,
because crowding across complex increases step by step, thus follow the trend K1 > K2 > K3 > K4.
The correct plot of logK vs x (K = stepwise stability constant) is A
87
Coordination Chemistry
94
Organometallic Compounds
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
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
(b) Mn and Fe
95
Organometallic Compounds
(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.
(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
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
14.The catalyst involved in carrying out the metathesis of 1-butene to give ethylene and 3-hexene
is:
97
Organometallic Compounds
(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
(d) (B) and (D) only
98
Organometallic Compounds
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
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)]-
(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
(d) 6 and 1 CH
29 For the following molecule :
101
Organometallic Compounds
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
D iv heck coupling
102
Organometallic Compounds
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)
32.Which one of the following will NOT undergo oxidative addition by methyl iodide?
(a) [Rh(CO)2I2]-
(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
103
Organometallic Compounds
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.
(d) increase with the presence of electron donating substituent on the olefin.
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
(a) 4.0
(b) 3.5
(c) 3.0
(d) 2.5
45. The correct statement regarding terminal/bridging CO groups in solid Co4(CO) 12 and Ir4(CO)
12 is
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
48. Subsitution of L with other ligands will be easiest for the species
(a)
(b)
(c)
107
Organometallic Compounds
(d)
49. Reaction of Ph2PCH2CH2PPh2 with [RhCl(CO)2]2 in a 2:1 molar ratio gives a crystalline solid
A. The IR spectrum of complex A shows νco at 1985 cm-1. The 31P(1H) NMR spectrum of A consists
of two doublets of doublets of equal intensities (103Rh is 100% abundant and I =1/2 ). The
structure of complex A is
(a)
(b)
(c)
(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]
108
Organometallic Compounds
(c) [Mn(CO)5] +
(d) [V(CO)6] –
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-
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
54. The compound [Re2(Me2PPh) 2CI4] (M) having a configuration of ϭ2π4δ2δ*2 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
109
Organometallic Compounds
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) intramolecular exchange between the ethylene ligands
(c) intermolecular exchange between the ethylene ligands
(d) change in hapticity of the cyclopentadienyl ligand
(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
(c) D4h and D3h
(d) D3h and D4h
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
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.
(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
(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
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
The correct statements are
(a) A, B and C
(b) A, B and D
(c) B. C and D
(d) A, C and D
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
(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
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
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
82. The reductive elimination of Ar-R (coupled product) from A is facile when
(a) R = CH3
(b) R = CH2Ph
(c) R CH2COPh
(d) R = CH2CF3
117
Organometallic Compounds
84. With respect to and bonding in Pt III in the structure given below, which of the following
represent the correct bonding diagram
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.
(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
91. The number of valence electrons provided by [Ru(CO)3] fragment towards cluster bonding is
(a) 1
(b) 14
(c) 6
(d) 2
(a) A and D
(b) B and D
(c) B and C
120
Organometallic Compounds
(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
94. The approximate positions of νco bands (cm-1) 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
[CSIR-JUNE 2016]
95. Identify the species, those obey the 18 electron rule, from the following:
(a) A and B
(b) B and C
121
Organometallic Compounds
(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.
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
122
Organometallic Compounds
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
(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
123
Organometallic Compounds
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
124
Organometallic Compounds
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
(d) 2 to 4
125
Organometallic Compounds
(c) cyclohexene
(d) 1-butene
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
[Mn(η2-B3H8)(CO)4] are
(a) closo and nido
127
Organometallic Compounds
(a) D2C=CD2
(b) D3C-CD3
(c)
(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
(a) A and B
(b) B and C
(c) C and D
(d) A and D
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,
129
Organometallic Compounds
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
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
(a) dz2
(b) dxy
(c) dxz
(d) dyz
126. In the complex [Pd(L-L)(Me)(Ph)], the bisphosphine (L-L) that does not allow reductive
elimination of PhMe is
(a)
(b)
131
Organometallic Compounds
(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
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)
(a) (C) < (A) <(B)
(b) (A) < (B) < (C)
(c) (B) < (C) < (A)
(d) (C) < (B) < (A)
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)
(a) B and C
(b) A and F
(c) A and D
(d) C and E
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
134
Organometallic Compounds
(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.
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
135
Organometallic Compounds
correct answer is
(a) A and C
(b) B and C
(c) A and B
(d) B Only
(a)
136
Organometallic Compounds
(b)
(c)
(d)
140. Match the following complexes with their vCO stretching frequency
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
(b)A>B ;C<D
(c) A<B ;C>D
(d) A<B ; C<D
137
Organometallic Compounds
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
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
138
Organometallic Compounds
(a) Br>I>F>Cl
(b) F>Cl>Br>I
(c)F≈Cl≈Br≈1
(d) I>Br>Cl> F
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
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
155.The rate-determining step in the catalytic synthesis of acetic acid by Monsanto process is
(a) oxidative addition of CH3I to [RhI2(CO)2]-
(b) migration of CH3 group to CO of [RhI3(CO)2(CH3)]-
(c) loss of CH3COI from [RhI3(CO)2(COCH3)]-
(d) coordination of CO to [RhI3CO(COCH3)]-
157. The main product of nucleophillic attack of H- on the complex ion given below is
141
Organometallic Compounds
(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
142
Organometallic Compounds
(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
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
144
Organometallic Compounds
shows three STRONG bands at 1986, 1935 and 1601 cm-1 . The correct structure of 'A' is
(a)
(b)
(c)
(d)
145
Organometallic Compounds
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]8
B. [𝑶𝒔𝟔 (𝑪𝑶)𝟏𝟖 𝑷]8
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
(a) (b)
(c) (d)
(a)
(b)
(c)
(d)
171. The structure of the reactive intermediate generated by the reaction of CHCl3 and KOH is
(a)
(b)
147
Organometallic Compounds
(c)
(d)
173. What is the order of decreasing carbonyl stretching frequencies in the following species (A-
D)? A. [Mn(CO)6]+ B.[Os(CO)6]2+ C. [Ir(CO)6]3+ D. Free CO
(a) B>A>C>D
(b) D>C>B>A
(c) A>B>C>D
(d) C>B>D>A
175. The reaction of MoCl2 with [Et4N]Cl in dil. HCl and EtOH produces a dianionic hexanuclear
metal cluster.
A. The cluster is [Mo6Cl14]2- .
B. The cluster has 136 valance electrons.
C. Each metal center has 4 metal-metal bonds.
Identify the correct statement(s) about the cluster.
(a) B only
(b) A and C only
(c) B and C only
(d) A, B and C
178. The pair of complexes/ions that does not obey the 18-electron rule, is
(a) [V(CO)6] and [Ti(Cp)2Cl2]
(b) [Mn(Br)(CO)5] and [Mn(CO)5]–
(c) [Co(CO)3PPh3]– and [Co4(CO)12]
(d) [Fe(CO)5] and [Fe2(CO)9]
149
Organometallic Compounds
180. The number of unpaired electrons in [Cp2Fe], [Cp2Ni] and [Cp2Co] complexes are, respectively,
(a) 0, 0 and 1
(b) 0, 2 and 1
(c) 0, 1 and 2
(d) 2, 2 and 1
182. Five moles of [B9H14]– react with two moles of B5H9 at 85 oC resulting in the evolution of nine
moles of H2 and the formation of a monoanionic borane cluster that has a
185. The number of skeletal electron pairs (SEP) and the cluster type for [B10H10]2- and [B6H9]-,
respectively, are
(a) 11, closo and 8, nido
(b) 11, nido and 8, nido
(c) 10, closo and 6, arachno
(d) 10, closo and 8, nido
186. The correct option for the oxidation state(s) of Nb in the cluster Na4[Nb6Cl18] is
(a) Two are in +3 state and four are in +2 state
(b) All are in +2 state
151
Organometallic Compounds
187. The compound shown below is a 48-electron metal cluster (not counting M-M bonds). The
metal M is
(a) V
(b) Fe
(c) Mn
(d) Cr
188. In the oxidative addition of trans-[IrCl(CO)(PPh3) ] with H2 (path A) and with CH3I (path B),
the d-orbitals involved in the electron transfer from iridium to H2 and CH3I, respectively, are
189. [Co(NH3)5(X)]Cl2 (1) on reaction with aqueous NH3 followed by addition of NaNO2/conc. HCl
yields [Co(NH3)5(Y)]Cl2 (2). Reaction with NaNO2 results in [Co(NH3)5(Z)]Cl2 (3). Complex 2
shows two spectral bands at 1310 and 1430 cm-1, whereas complex 3 shows the same at 1065 and
1470 cm-1. X, Y, and Z, respectively, are
(a) X = Cl; Y = NO2; Z = ONO
(b) X = H2O; Y = NO2; Z = ONO
(c) X = Cl; Y = ONO; Z = NO2
(d) X = H2O; Y = ONO; Z = NO2
152
Organometallic Compounds
190. The option showing both the complexes obeying the 18e- rule is
(a) [(ƞ5-C5H5)RuCl(PPh3)2] and [(ƞ5-C5H5)2ZrCl2]
(b) [IrCl(CO)(PPh3)2] and [Co2(CO)8]
(c) [Re(CO)5(PF3)]+ and [Ni(NH3)6]2+
(d) [(ƞ5-C5H5)(ƞ3-C5H5)Fe(CO)] and [(ƞ3-allyl)Mn(CO)4]
(a) (i)
(b) (ii)
(c) (iii)
(d) (iv)
(η5-C5H5)2 Fe 18
(η5-C5H5)2Co 19
(η5-C5H5)2Ru 18
(η5-C5H5)2Co+ 18
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
Since rate does not depend upon the concentration and nature of the ligand suggesting a dissociative
mechanism.
Since, the molecule is C2 -symmetric. So, two CO's will give two absorption band in IR spectrum.
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
161
Organometallic Compounds
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.
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
163
Organometallic Compounds
A= TVE =60
B (n×18) – TVE= 72 – 60= 12
metal-metal bond= B/2 =12/2= 6
?@8?A C8D
Bond order = B
= B
= 3.5
164
Organometallic Compounds
5+8+4+1 = 18
CH→4+1=5e
E
Co(CO)3→ 9+6=15e CH H⎯⎯⎯⎯⎯⎯& Co(CO)3
But, CH₂→4+2=6e
Ni(CO)2 →10+4=14e not isolobal
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).
2x+0 = -2
x=-2/2 , x = -1
M-M bond =1
[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
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.
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 .
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.
74. Correct option is (a)
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)
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)
174
Organometallic Compounds
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.
[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.
81. Correct option is (b)
[Ru6(C)(CO)17]
176
Organometallic Compounds
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
TEC=76
PEC =76-60=16
PEC/2=16/2 =8= (5+3)=(n+3) Arachno
All the products are possible but possibility of (4) is least as alkene doesnot undergo reductive
elimination reaction easily as compare to alkane.
Example of migratory insertion reaction in which alkyl group insert to CO. A new ligand create acycl
group and a vacancy is created which is occupied by new ligand.
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.
179
Organometallic Compounds
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
μ2 CO=1850-1750 cm-1
In this complex M-M bond order = 1 and two types of CO's terminal as well as ꭒ2 -bridging. So,
νco band lies in both range.
181
Organometallic Compounds
TVE= (9 × 2) + (8 × 2) + (2 × 11) + (4 × 2)
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.
100. Correct option is (b)
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
Thus, in Ni(Cp)2 there are highest number of electrons in e*1g . Hence, it has highest M-C bond
183
Organometallic Compounds
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.
During fluxional axial ligands are exchanged with equatorial ligand. Hence,
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
107. Correct option is (b)
Atoms 1 to 6 are the prism atoms, 7 to 9 are H-atom are equatorial hydrogen.
Na [Mn(CO)5] + CH₂=CH-CH₂-Cl →
Mechanism:
[(η5-Cp) Fe (η6-C6H6)]+
Actually formed but does not give reaction This can give reaction but not formed
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)
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.
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.
For reaction A:
For Reaction B:
199
Organometallic Compounds
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.
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-
12e electrons are in the lower orbitals and remaining five electrons occupies the orbital as follows.
∆
[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)
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
For compound
Here Mo forms the cluster and Cl is present in bridging and axial positions, such that it donates all
its valence electrons to the cluster,
Thus electrons donated by Cl = 7
Each Mo donates 6 Valence electron.
Total Valence Electrons = (6´Valence electrons from Mo)+(14´ valence electrons from Cl)+(2 for
negative charge)
TVE = (6´6+14´7+2) = 136
2. [IrCl(CO)(PPh3)2] = 9 + 1 + 2 + 4 = 16e-
[Co2(CO)8] = 18 + 16 = 34e-
3. [Re(CO)5(PF3)]+ = 7 + 10 + 2 - 1 = 18e-
[Ni(NH3)6]2+ = 10 + 12 – 2 = 20 e-
4. [(ƞ5-C5H5)(ƞ3-C5H5)Fe(CO)] = 5 + 3 + 8 + 2 = 18e-
[(ƞ3-allyl)Mn(CO)4] = 3 +7 + 8 = 18e-
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
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
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
(a)
217
Main Group Elements
(b)
(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
218
Main Group Elements
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.
(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.
219
Main Group Elements
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
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.
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
(a) N₂O
(b) NO
(c) N2O3
(d) N2O5
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
(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
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
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.
(a)
(b)
222
Main Group Elements
(c)
(d)
(a)
(b)
(c)
(d)
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
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
224
Main Group Elements
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+
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
225
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
(a)
226
Main Group Elements
(b)
(c)
(d)
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)
227
Main Group Elements
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
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
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
64. The metal iodide with metallic lustre and high electrical conductivity is
(a) NaI
(b) CdI2
(c) LaI2
(d) BiI3
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]-
229
Main Group Elements
(c) [B4H10.NMe3]
(d) [B4H10.NMe3] and [BH2(NMe3)2]+ [B3H8]-
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
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
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)
74. Among the elements Zn, Ga, Ge as As, the one with the lowest first ionization energy is -
(a) As
(b) Zn
(c) Ga
(d) 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,
(a) XeF2 and XeF4
(b) XeF4 and XeF6
(c) XeF6 and XeF4
(d) XeF6 and XeF6
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
(a) A, B and C
(b) A and B
(c) D only
(d) B. C and D
231
Main Group Elements
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
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
The correct match is
(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
232
Main Group Elements
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
89. The common heptacity observed for coordination of C60 to a metal center is
(a) 2
(b) 4
(c) 5
(d) 6
(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
(a) A, B and C
(b) A, B and D
(c) B, C and D
(d) 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)
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
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
102. The reaction of HF with SnO produces P and with SnCl4 produces Q. Reaction of one of them
(P,Q) with NaF yields the species Na4[Sn3F10]. Among the following,
A. [Sn3F10]4- is obtained from P.
B. In the solid state, P exhibits a ring structure.
C. Stereogenic lone pairs of electrons are presents in both P and Q.
D. Q is weaker Lewis acid than P.
Identify the correct statements.
(a) A and B only
(b) C and D only
(c) A,B and C only
(d) B,C and D only
104. In the stratosphere, the radical Cl– produced from chlorofluorocarbons reacts with O3 as
follows
Cl– + O3® X + colorless gas
2X ® X2
X2® Cl– + Y
X, Y are respectively
105. Among Si3N4, α-BN, AIN and (SN)x, the compound with the highest conductivity is
(a) Si3N4
(b) α-BN
(c) AIN
(d) (SN)x
106. The Ionization energies (IE1 to IE5) of ‘s’ and/or ‘p’ block elements (X,Y and Z) are given
below.
IE1 IE2 IE3 IE4 IE5
(kJ mol–1) (kJ mol–1) (kJ mol–1) (kJ mol–1) (kJ mol–1)
X 1086 2353 4620 6223 37830
Y 800 2427 3060 25030 32830
Z 496 4562 6910 9543 13350
(a) X=2; Y=3; Z=4
(b) X=4; Y=1; Z=1
(c) X=4; Y=3; Z=1
(d) X=1; Y=3; Z=4
107. The number of oxygen atoms bonded to each phosphorus centre in P4O6 and P4O10
respectively, are
(a) 4 and 5
(b) 3 and 5
(c) 3 and 4
(d) 5 and 4
238
Main Group Elements
108. X, Y and Z are three p-block elements in the second row of the periodic table, with electron
affinities (in kJ/mol) of –15, –142 and –333, respectively. The correct statement among the
following, is
(a) Y has the highest first ionization energy.
(b) X has the most number of p-electrons.
(c) X has the highest proton affinity
(d) Z has the highest electronegativity.
109. In the process of desulfurization of flue gas, SO2 is passed through an absorber containing
slaked lime in the presence of O2. The final product is
111. In the solid state, methyl lithium is tetrameric and has a Li4 core. The correct statement about
the structure and bonding in methyl lithium is
(a) Each methyl anion is bridging between two Li-centers via 3-center-2-electron bonding.
(b) Each methyl anion binds to three Li centers via 4-center-2-electron bonding.
(c) It possesses a 2-center-2-electron bond.
(d) Each methyl anion is terminally bound to each Li-centre.
113. The total number of six membered rings in the polycyclic compounds P4(NMe)6 and
P2(N2Me2)3 is
(a) 7
(b) 6
(c) 5
(d) 4
114. The difference in second ionization energies of Li/Na, Be/Mg, B/Al and N/P are X1, X2, X3 and
X4, respectively. The correct order of the difference in the second ionization energies is
(a) X1 > X4 > X3 > X2
(b) X1 > X2 > X3 > X4
(c) X4 > X3 > X1 > X2
(d) X1 > X3 > X4 > X2
115. Completer hydrolysis of XeF6 gives P, whereas alkaline hydrolysis of XeF6 gives Q and R as
the major products. P, Q, and R, respectively, are
(a) 𝑿𝒆𝑶𝟑 , 𝑿𝒆𝑶𝟒$𝟔 , 𝒂𝒏𝒅 𝑿𝒆
(b) 𝑿𝒆𝑶𝟒 , 𝑯𝑿𝒆𝑶𝟒$ 𝟔 , 𝒂𝒏𝒅 𝑿𝒆
(c) 𝑿𝒆𝑶𝟒 , 𝑿𝒆, 𝒂𝒏𝒅 𝑿𝒆𝑶𝟒$ 𝟔
(d) 𝑯𝑿𝒆𝑶𝟒$ 𝟔 , 𝑿𝒆𝑶 𝟑 , 𝒂𝒏𝒅𝑿𝒆𝑶 𝟒$
𝟔
240
Main Group Elements
Compounds Uses
(A) Na3PO4 Water softener
Because P-O bond very strong affinity very high not easily break. So, R-O bond break.
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.
245
Main Group Elements
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.
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.
N3P3Cl3F3(C) = 3 isomer
248
Main Group Elements
C2B10H12 is show three isomeric derivative which is depend on the the temperature.
249
Main Group Elements
The reason is that HNO3 is better oxidising agent than H2SO4, also acts as dehydrating agent.
CaB6 and CsCl both have BCC like structure, the B6 cluster is present at the body center of Ca lattice.
Be2Cl4 = Planar
Be2Cl4 = Planar
GaI[GaIIICl4]
Ga2Cl4 = tetrahedral , No M-M bond
In Siloxanes
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
• Bigger metal hydrides are usually interstitial hydrides as H- can be trapped in their bigger voids.
• [TcH9]-2 is trigonal tricapped prismatic.
Dithionite
S2O4-2
2x = 8-2
x = +3
Dithionate
S2O6-2
2x = 12-2
x = +5
(Gypsum)
110. Correct option (d)
The valence electronic configuration is given by
Be B C N
2s2 2s22p1 2s22p2 2s2 2p3
Second ionization energy means the energy required to remove an electron from the mono-ionic species,
The valence electronic configuration of mono-ionic species is given by
Be+ B+ C+ N+
2s1 2s2 2s22p1 2s2 2p2
Now due to higher effective nuclear charge in N+ it becomes very difficult to remove an electron further,
this makes 2nd ionization enthalpy of N highest among all.
This will be followed by B as it has attained a stable configuration of 2s2
Next will be C and least will be Be
Thus the order will be = N > B > C > Be
267
Main Group Elements
P4(NMe)6 → 4 rings
P2(N2Me2)3 → 3 rings
Total rings = (4 + 3) = 7.
Since the second ionization energy for lithium is very high thus the difference X1 will be more too.
While X2 will be least as after losing second electron, alkaline metals gain stable noble gas
configuration.
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 2012]
3. In ‘carbon-dating’ application of radioisotopes, 14 C emits
(a) β-particle
(b) α-particle
(c) γ-radiation
(d) Positron.
CSIR SEP 2012
4. For the following nuclear decay series segment,
𝟐𝟑𝟒 𝟐𝟑𝟒
𝟗𝟎𝑻h ®®® 𝟗𝟎𝑻𝒉
the overall emitted particles are
(a) one β one α and one neutron
(b) two β and one α
(c) three β
281
Nuclear Chemistry
7. For a low energy nuclear reaction, 24Mg (d, α) 22Na, the correct statements from the following
are
(a) Kinetic energy of d particle is not fully available for exciting 24Mg.
(b) Total number of protons and neutrons is conserved
282
Nuclear Chemistry
(c) Q value of nuclear reaction is much higher in magnitude relative to heat of chemical reaction
(d) Threshold energy is ≤Q value.
8. The particles postulated to always accompany the positron emission among are:
(A) neutrino,
(B) anti-neutrino,
(C) electron,
(a) A, B and C
(b) A and B
(c) A and C
(d) B and C
[CSIR DEC 2015]
9. Spin motion of which of the following gives magnetic moment
A. Electron;
B. Proton;
C. Neutron
Correct answer is:
(a) A and B
(b) B and C
(c) A and C
(d) A, B and C
12. Choose the correct statement for magnitude of threshold energy of an endoergic nuclear
reaction between stationary nucleus and a moving projectile.
(a) It is greater than 'IQI' of nuclear reaction.
(b) It has to be more than kinetic energy of a projectile.
(c) It is less than 'IQI' of nuclear reaction.
(d) It has to be equal to kinetic energy of a projectile.
13. 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
Correct statement(s) is/are:
(a) A and B
(b) B and C
(c) A and C
(d) C only
16. The set among the following in which all numbers are magic numbers of nucleons is
(a) 20, 28, 50 and 126
(b) 24, 28, 82 and 126
(c) 20, 50, 80 and 184
(d) 28, 50, 82 and 180
[CSIR DEC 2019]
17. Identify from following the products of K-electron capture by the nucleus:
(A). neutron
(B). neutrino
(C). positron
Answer is
(a) A only
(b) A and B
(c) C only
(d) B and C
[CSIR 2020]
18. Consider the nuclear reaction
234
92X + β +α → Y+ γ+ 2β+
Y is
(a) 92Y238
(b) 91Y238
285
Nuclear Chemistry
(c) 93Y236
(d) 94Y238
[CSIR JUNE 2023]
19. Statements A-D below pertain to the given decay series,
A. The radionuclide (D) is formed by two successive b-particle emissions from the radionuclide
(B).
B. The radionuclide (E) is formed by successive b-particle and a-particle
C. The atomic number of the radionuclide (C) is 91.
D. The atomic number of the radionuclide (D) is 90.
The correct statements are
(a) A and C only
(b) Band D only
(c) C and D only
(d) A, B and C only
*, -e#!" (positron) */
*+Ne %⎯⎯⎯⎯⎯⎯⎯⎯' ,F ;
#
*/ -e$" (β- particles) */
0 C %⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯' 2N ;
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 𝟏n
𝟏 + e- → 𝟎 + ῡe
Proton electron neutron neutrino
Henuce, the products are neutron and neutrino
ϒ is a form of energy that is released when a neutron collides with Uranium atom.
290
Inorganic Spectroscopy
291
Inorganic Spectroscopy
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 nuclear 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).
4. In the 19F NMR spectrum of PF5 , the number of signals and multiplicity, at room temperature
are
(a) One, singlet
292
Inorganic Spectroscopy
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
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)
293
Inorganic Spectroscopy
(a) 3 and 30
(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)
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
294
Inorganic Spectroscopy
12. Find out the number of lines in the 31P NMR signal for diagram
(a) 3
(b) 6
(c) 18
(d) 90
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.
295
Inorganic Spectroscopy
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
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
23. The 119Sn NMR chemical shift (approximately in ppm) corresponding to (ղ5-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
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
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
300
Inorganic Spectroscopy
(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
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
(a)
(b)
(c)
302
Inorganic Spectroscopy
(d)
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
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
304
Inorganic Spectroscopy
(a)Two
(b)Four
(c)Six
(d)Eight
46. The 1H-NMR spectrum of [(C5H5)2Fe (CO)2] exhibits two peaks of equal intensity at room
temperature , but four resonances of relative intensities 5:2:2:1 at lower temperature. The
hapticities of C5H5- are
(a) h5andh1
(b) h5and h3
(c) h3and h1
(d) h3and h3
305
Inorganic Spectroscopy
(a) 14N7
(b) 31P15
(c) 24Mg12
(d) 29Si14
49. The electron paramagnetic resonance spectrum from among the following, which represents a
metal ion with S = 1/2 in rhombic symmetry,
(a) IV
(b) III
(c) II
(d) I
51. The 19F NMR spectrum of [XeF5]- ion shows [129Xe, I = ½, 26.5% abundance]
(a) A doublet with satellite peaks
(b) A triplet and a quartet with satellite peaks for both
(c) A doublet and a quintet with satellite peaks for both
(d) A singlet with satellite peaks
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.
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
trans-[IrCI(Co)(PPh3)2] will give singlet of 2P.
[Ir(PPh3)4]+ will give singlet of 4P.
0 1
mICH = ± ,, mlN =1; mlCu = ,,
+15 6!
= ,34 !
𝑒𝑉
+15 6!
= 2.5 × 105 = 017×710.+
,.+×017×710.+×0/"
E=G +15
= 24.57 × 101 eV= 25 keV
4H1 2N15 2F 1H
0
Equatorial F= 2x 2 x , + 1 = 3 , n=2 (axial F)
0
Axial F= 2x 2 x , + 1 = 3 , n=2 (Equatorial 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
EPR spectroscopy generally used for the species have one or more unpaired electron.
Cu(II) are EPR active because non-paired electron.
as 74% Xe are NMR inactive hence a singlet of five fluorine and due to 26% nuclei a doublet of
satellite.
(2x2x1/2+1) = 3 triplet
So, total number of line 2+3=5
31
P {1H} → (2NI+1)=[2×2×1/2+1]=3 (triplet)
31
P {1H} → (2NI+1) = (2x2x1/2+1)=3 (triplet)
mer-[M(PR3)3Cl3]
gǁ > g ╧ >g2
the evidence that Cu on is present in tetragonally distorted octahedral field,
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
In tetragonally elongated Cu(II) complex, more electron density is along dz2 orbital hence 𝑔∥ > 𝑔$
Ground state for tetragonally compressed Cu(II) complexes is dx2-y2 .
At low temperature the bonds are rigid and thus they don’t show fluoxional behaviour thus we get
NMR peaks of ratio 2:2:1 for one ring and 5 protons of h5 ring give peak at same chemical shift
thus we get 5:2:2:1 at very low temperature.
At room temperature the rings show ring whizzing and thus all 5 protons of h1 ring becomes
equivalent and other h5 ring gives one peak at another chemical shift thus giving NMR peak of
ratio 1:1.
For a nucleus to be NMR active: Either atomic no. should be odd or atomic mass should be odd or both
should be odd. If both atomic no and atomic mass are even then nucleus is NMR inactive, I = 0.
Here, 24Mg12 has both even atomic no and atomic mass.
49. Correct option (a)
Number of hyperfine lines = 2NI + 1; where N is the number of equivalent nuclei; I is the spin
(provided).
2𝑁𝐼 + 1 = 8
7
2𝑁 × + 1 = 8
2
𝑁= 1
Oxidation state of V in [VO]2+ = +4; which means V is in d1 configuration with 1 unpaired electron.
Thus, [VO]2+ unit is the correct answer.
51. (d)
The geometry of [XeF5]- is pentagonal planar, where all the F atoms are equivalent, hence a singlet peak
will be observed.
322
Inorganic Spectroscopy
129
Xe (I = ½), being an active nucleus, with very less abundance of 26.5%, will show two satellite peaks
of very low intensity.
(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+
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)
326
F-Block Elements
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)
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
327
F-Block Elements
19.The metallic radii are abnormally high for which of the following pairs?
(a) Eu, Yb
(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
22. The g values for Ce+3 (4f1) and Pr+3 (4f2) are, respectively
(a) 3/7 and 2/5
330
F-Block Elements
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
28. Match fluorescence colours given in column A with lanthanide ions given in Column B
Correct match is
(a) (i)-(a); (ii) - (c); (iii)-(b); (iv) - (d)
332
F-Block Elements
(c) Eu and Tb
(d) Sm and Eu
[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
(d) +3 only
36. The calculated magnetic moment (B.M.) for the ground state of a f5 ion is
(a) √𝟑𝟓 / 7
(b) √𝟑𝟓
(c) √𝟑𝟓 /14
(d)35/14
B. U𝐎𝟐"
𝟐 is a hard acid.
D. Both the 5f and 6d orbitals of U are involved in bonding with the 2p orbitals of oxygen atom.
The correct statements for U𝐎𝐧"
𝟐 are
41. The calculated magnetic moment of Eu3+ (4f6) is 0 (zero)BM. The experimental value is 3.4-3.6
BM at 298K. The deviation is due to the
(a) Mixing of 4f and 4d orbitals
(b) Large spin-orbital coupling constant (𝝀)
(c) Large orbital angular momentum
(d) Populated ground and excited state
42. The absorption spectrum of Ln3+ is normally sharp and weak in intensity. However, Sm3+ (4f5)
in dil. acidic solution shows a broad and moderately intense transition at 495 nm. This transition
is
(a) 6H5/2 →6H7/2
(b) 6H5/2 →4G5/2
(c) 6H5/2 →6H9/2
(d) 4G5/2 →4G7/2
(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 ꞵ-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.
Smaller the size of Lu3+ ion, higher will be the partition coefficient.
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
L=3+2+1+0-1-2-3
0 1 2 3
339
F-Block Elements
S P D F
J=|L+ S|……|L-S|
=|3+3|….. |3-3|
=6 0
7
F6 7 F0
Ground state term 7F0
(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
341
F-Block Elements
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.
21. Correct option is (a)
[UO2(NO3)3 ]-1
Ce+3 = f1
L=3
S=½
J=|L-S| for orbital less then half filled
J=|3-½|=5/2
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
342
F-Block Elements
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
Hence μ = .J(J + 1) = 0
(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
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.
• Gd+3 (f7) and Lu+3 (f14) follow spin only formula µ = !.𝑛(𝑛 + 2)
Here, S = 2, L = 6 and J = 8,
Solving for 𝑔 will give, 𝑔 = 1.25
Hence 𝜇233 = 10.6
S = 5/2
L=5
1
J = L – S = 5− %
4561 1
= %
=%
µeff = g .𝐽(𝐽 + 1)
7(7"4)68(8"4)"9(9"4)
g=1+ %9(9"4)
%
on putting values of S, L and J we get, g = :
thus, putting values of g and J in formula of µeff, we get
% 1 :
µeff= A ×
: % %
% ;1
= :A0
√;1
= :
The high Energy states will populate and increase observed magnetic moment due to LS coupling
=
S = % = 3, S.M = 2S + 1 = 2 ´ 3 + 1 = 7
L = 3® F
7
J = L–S = 3–3 = 0 F0
S = n/2 = ½
L=3
J = 3 + 0.5 = 3.5
In general, experimental and calculated values of magnetic moment agree well, based on Russell-
Saunders coupling and large spin-orbit coupling constants, as a result of which only lowest J states are
populated. This is not true for Eu3+ and Sm3+.
For Eu3+ (f6) ion, the spin-orbit coupling constant 𝜆 ≈ 300cm-1, only slight greater than kT (≈ 200 cm-
1
), the ground state of the f6 ion is 7F0, but the states 7F1 and 7F2 are also populated to some extent and
give rise to the observed magnetic moment.
S = 5/2; 2S+1 = 6
L = +3+2+1+0-1 = 5 → H
1 1
J=5−%=%
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
7. Among the following pairs, those in which both species have similar structures are:
(A) N3- , XeF₂
(B) [ICl4]-, [PtCl4] 2-
350
Chemical Bonding
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)
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
14.When a hydrogen 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
18. The molecule in which the bond order increases upon addition of an electron
(a) O2
(b) B2
352
Chemical Bonding
(c) P2
(d) N2
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
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
25. The correct schematic molecular energy diagram for SF6 molecule is:
(a)
(b)
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Chemical Bonding
(c)
(d)
CSIR JUNE 15
27. For the oxidation state(s) of sulphur atoms in S2O, consider the following
A. -2 and +4
355
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
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
(A) [NiCl4] -2 (tetrahedral)
(B) IF7 (pentagonal bipyramidal)
(C) [CoF6] -3 (octahedral)
(D) Fe(CO)5 (trigonal bipyramidal)
(a) B and C
(b) B and D
(c) C and D
(d) A and D
(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
(a) σ1s2 σ1s*2 σ2s2 σ2s*2 σ2p2 π2p2
(b)σ1s2 σ1s*2 σ2s2 σ2s*2 σ2p2 σ2p*2
(c) σ1s2 σ1s*2 σ2s2 σ2s*2 π2p2 σ2p1 σ2p*1
(d) σ1s2 σ1s*2 σ2s2 σ2s*2 π2p4
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
(b) 120°
(c) 60°
(d) 90°
(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
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
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
Column I Column II (𝝀𝒎𝒂𝒙 , 𝒏𝒎)
(a) non-donor (i) 520
(b) weak donor (ii) 500
(c) strong donor (iii) 450
(d) π electron donor (iv) 360
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
(a) A. B and D
(b) B and C
(c) B, C and D
(d) B and D
52. Arrange the following molecules in order of increasing fundamental vibrational frequencies
(a) O2-2 < O2-< O2 < O2+
(b) O2 < O2+ < O2- < O2-2
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Chemical Bonding
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
57. The magnitude of bond angles in gaseous NF3 , SbF3 and SbCl3 follow the order
(a)NF3 >SbF3 > SbCl3
(b)SbCl3> SbF3> NF3
(c)SbF3> SbCl3> NF3
(d)NF3 > SbCl3 > SbF3
58. The species for which the shapes (geometry) can be predicted by VSEPR theory is/are
(A) [PtCl4]2-
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Chemical Bonding
(B) [TeCl6]2-
(C) PF3 and SF6
Answer is
(a) A and C
(b) B and C
(c) C only
(d) 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
62. The total bond order between adjacent carbon atoms of benzene is
(a) 0.5
(b) 2
(c) 1.5
(d) 2.5
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
(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
66. Consider the statements about the following species, ClF,[CIF2]+, CIF3,[CIF4]+ and CIF5.
A. There are 9 lone pairs of electrons on the chlorine atoms in the five species.
B. The species [ClF4]+ has a tetrahedral shape.
C. The compound [ClF4]+ is a very strong fluorinating agent.
The correct statement are:
(a) B and C only
(b) A and C only
(c) A and B only
(d) A,B and C
68. The statement(s) that correctly describe (s) the molecular orbital (MO) diagram of HO
(hydroxyl radical) is/are (consider the O-H bond to be along the axis)
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Chemical Bonding
69. Considering nitrogen as a central atom, the structures of H3C–N=C=S and H3Si–N=C=S
respectively, are
(a) bent and linear
(b) linear and linear
(c) bent and bent
(d) linear and bent
70. Among SF4, ClO4–, FClO3 and IF4+, the number of species having “see-saw” shape is
(a) 2
(b) 1
(c) 3
(d) 4
71. Consider the following reaction scheme and the related statements.
$%&'()')(*%)+,*%)+
BrF 4⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯6 Br2(g) + X (T shaped geometry)
&./0 %)+%1,*%)+
X 4⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯6 Y (cation) + Z (anion)
A. X, Y and Z have the same number of lone pairs of electrons.
B. Y has a bent shape.
C. Z is sp3 hybridized and has tetrahedral shape.
D. X is used as a non-aqueous solvent
73. According to VSEPR theory, the geometries of FClO and F5IO, respectively, are
(a) Linear and octahedral
(b) Tetrahedral and octahedral
(c) Tetrahedral and capped octahedral
(d) Trigonal bipyramidal and capped octahedral
74. According to VSEPR theory, the shapes and geometries of SeF4 and [BrF4]-, respectively are
(a) See-saw and trigonal bipyramidal; see-saw trigonal bipyramidal
(b) Square planar and octahedral; square planar and pentagonal pyramidal
(c) See- saw and trigonal bipyramidal; square planar and octahedral
(d) Square planar and square bipyramidal; square planar and octahedral
The 3s, 3p of Sulphur and 2pz of fluorine are mixed to give ten MO's. Calculations indicate that four of
orbitals 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 1t1. 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 follows
Hence, the probable O.S. of 'S' are (0 and +2) from structure 'T' and (-2 and +4) from structure II.
4σ and 4π
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Chemical Bonding
Note: The lone pair of [SbCl6] 3- is steriochemically inactive and that of XeF6, is boderline of
stereochemically active and stereochemically inactive condition.
?72×5 52
Xe= ?
= ?
=3+1=4→sp3 (Tetrahedral)
272×> 54
SO3 = ?
= ?
=3→sp2 (Trigonal planar)
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+ = 2
=3
8- 3
Bond order of O2+ = 2
= 2.5
7- 2
Bond order of N2+ = 2
= 2.5
5- 2
Bond order of C2+ = 2
= 1.5
•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'.
1O
Hybridisation = 1 + 2 = 3 i.e. sp²
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.
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)
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Bioinorganic Chemistry
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
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
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 bound 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
15. The metal ions present in the active site of nitrogenase enzyme co-factor are
(a) Fe, Mo
(b) Fe, W
(c) Fe, Cu
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Bioinorganic Chemistry
(d) Fe, Ni
16. For the metalloprotein hemerythrin, the statement that NOT TRUE is
(a) there are two iron 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.
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
20. Oxidised form of enzyme catalase (structure A); prepared by the reaction of [Fe(P)]+
(P = porphyrin) with H2O2 has green color because
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
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.
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
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Bioinorganic Chemistry
(c) 3, 3 and 2, 2
(d) 2, 4 and 3,2
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
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Bioinorganic Chemistry
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.
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 (ⱽo-o. in cm-1) of O2, is 1580. The ⱽo-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
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Bioinorganic Chemistry
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
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Bioinorganic Chemistry
40. In human body cis- platin 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
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
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]
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Bioinorganic Chemistry
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
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
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
(a) (A) only
(b) (C) Only
(c) (D) Only
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Bioinorganic Chemistry
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
Correct matches:
(a) A-III-Z, B-I-Y, C-II-X
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Bioinorganic Chemistry
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
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
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Bioinorganic Chemistry
(d) A only
(c) B, C only
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
(a) A, Band C
(b) A, C and D
(c) A, B and D
(d) B and C only
63. The correct match for the drug molecules in the Column A with their medicinal use in Column
B is
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
(a) A and B
(b) B and D
(c) C only
(d) C and D
[CSIR 2020]
66. The complex (es) showing activity against cancerous cells is/are
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)]
69. Match the items of column I with the applications given in column II
70. Match the iron and copper proteins with biological function in the table below:
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
74. The number of electrons involved in the enzymatic action of cytochrome c oxidase, carbonic
anhydrase and photosynthetic oxygen evolving complex, respectively, are
(a) 2,0,4
(b) 4,0,4
(c) 4,1,0
(d) 2,0,2
76. The statement regarding the properties of Type I blue copper proteins that is true is
(a) The Cu(II) centre is bound to His and Cys amino acids only
(b) In the EPR spectrum, the A1 value in Blue copper proteins is greater than the A1 value of free
Cu(II) ion.
(c) There is an intense absorption band in the electronic spectrum at lmax » 600 nm and emax » 100
times greater than the emax of aqueous Cu (II) ion.
(d) It exists as a pair of Cu (II) centers.
77. For the four active metal centres in cytochrome c oxidase shown below,
A. Electron transfer involves Heme and CuA while O2 binding involves Heme a2 and CuB.
B. O2 only interacts with CuB to form a Cu(II)–𝐎"𝟐 species with no role for both the heme.
C. Heme a is 5-coordinate species with an axial his ligation.
D. CuB is a monomeric 3-coordinate species while CuA is a dicopper species.
78. The following statements are given with respect to the copper-containing nitrite reductase.
A. It contains both Type-II and Type -III copper proteins
B. Type-I copper protein is involved in the electron transfer process.
C. Nitrite ion is reduced to NO
D. Nitrite ion is reduced to NH3
The option with correct statement
(a) A and B only
(b) B and C only
(c) A and C only
(d) A and D only
79. The oxy-hemocyanin exhibits a resonance Raman signal at 744 cm-1 for 16O-16O stretch,
following its excitation at 575 nm. The value of the 18O-18O stretch for an 18O2 substituted oxy-
hemocyanin, and the origin of the absorption band are
(a) 702 cm-1 and 𝑶"
𝟐 → 𝑪𝒖(𝑰𝑰) charge transfer
(b) 702 cm and 𝑶𝟐"
-1
𝟐 → 𝑪𝒖(𝑰𝑰) charge transfer
(c) 664 cm and 𝑶"
-1
𝟐 → 𝑪𝒖(𝑰𝑰) charge transfer
(d) 792 cm and 𝑶𝟐"
-1
𝟐 → 𝑪𝒖(𝑰𝑰) charge transfer
Hemoglobin met-hemoglobin
Zn= metalloezymes
μ-oxo-dimer (hematin)
Hemerythrin, one iron centre is penta coordinated and other is hexacoordinated and iron exist at
peractive site found in marine invertebrates.
Chlorophyll, 10 π electrons in
HEME, 11 π electrons in microcyclic ring
microcyclic ring
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Bioinorganic Chemistry
Deoxy . Hb Oxy Hb
413
Bioinorganic Chemistry
Fe+2 HS Fe+2 LS
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.
Here, step (2) shows attack of OH group with CO2, the product formed after step (3) shows later
interaction of CO2 with Zn metal.
Number of inorganic sulfur (sulfide) which do not belong to protein chain in ruberdoxin, 2-ferredoxin
and 4- ferredoxin are 0, 2, 4 respectively.
In DNA stand, cis-platin binds to two adjacent guanin bases (Not to cytosine bases)
•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
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.
(B) [Fe(CN)6]-3
Fe+3 → 3d5
(C) [NiCl4]2-
Ni+2 = d8 = t2g4 eg4
2 unpaired electron
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Bioinorganic Chemistry
(D) [Cu(NH3)4]2+
Cu+2 = t2g5 eg4
1 unpaired electron
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,
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)
Photo synthetic oxygen is the oxygen generated during photosynthesis, that means from water to O2
which will follow below reaction,
2H2O ⇄ O2 + 4H+ + 4e–
Thus total 4, 0 and 4 electrons are involved in the mentioned reactions.
In the EPR spectrum, A1 value of free Cu ion is greater than A1 value in blue copper protein. It exists as
single Cu centers.
2
𝜗∝
√7
𝝑𝑶𝟏𝟖 𝝁𝟏𝟔 𝟖
𝟐
𝝑𝑶𝟏𝟔
= 7𝝁𝑶𝟐
𝟏𝟖 = 7𝟗
𝟐 𝑶𝟐
>
𝜗𝑂32> = 7? × 744 𝑐𝑚"2 = 702 𝑐𝑚"2 .
5. 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
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Analytical Chemistry
(4) D, A and B
11. 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
(b). B, C and D
(c). C, D and A
(d). D, A and B
18. 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
19. 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
The correct answer is:
1. A only
2. B only
3. A and C
4. B and C
20. 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-2018
21. 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
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
The answer is
1. A and B
2. B and C
3. C and D
4. A and D
30. A solute S has partition coefficient (KD) of 5.0 between water and chloroform. A 50 mL sample
of a 0.050 M aqueous solution of the solute is extracted with 15 mL of chloroform. The extraction
efficiency for the separation is
(a) 50%
(b) 60%
(c) 30%
(d) 40%
31. The feature that incorrectly describes an ideal detector in gas chromatography, is
(a) The adequate sensitivity should be in the range of 10–8 to 10–15 g solute/s.
(b) It has a short response time that is independent of flow rate.
(c) It is non-destructive of the sample.
(d) There is a linear response to a 10-fold change only in the solute concentration.
32. In the differential scanning calorimetry plot of a polyethylene sample (given below), if the heat
of fusion is 68.4 cal/g, the percent crystallinity of the sample,
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Analytical Chemistry
(a) 100 %
(b) 55 %
(c) 68 %
(d) 79 %
(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 spectrofluorimetric laser may used as source
when two separate reactions converge to give same final product (target molecule) then the synthesis
mode is said to be Convergent synthesis
5.0 × 15
𝐸" = = 0.6
50 + 5.0 × 15
Thus extraction efficiency is 60%
%&.% )*+/-
= ./.& )*+ -
= 79 %