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12.co Ordination CompoundsExercise

This document provides examples and solved problems regarding coordination compounds. It discusses topics like: - Coordination entities and their oxidation states - IUPAC naming of coordination compounds - Types of isomerism exhibited by coordination compounds - Drawing structures of coordination compounds - Explaining differences in magnetic properties - Determining coordination numbers and complex structures The document contains 10 examples of problems involving topics like writing formulas, drawing structures, determining oxidation states, isomerism, stability, and magnetic properties of coordination compounds. The examples are solved to illustrate concepts in coordination chemistry.

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0% found this document useful (0 votes)
252 views34 pages

12.co Ordination CompoundsExercise

This document provides examples and solved problems regarding coordination compounds. It discusses topics like: - Coordination entities and their oxidation states - IUPAC naming of coordination compounds - Types of isomerism exhibited by coordination compounds - Drawing structures of coordination compounds - Explaining differences in magnetic properties - Determining coordination numbers and complex structures The document contains 10 examples of problems involving topics like writing formulas, drawing structures, determining oxidation states, isomerism, stability, and magnetic properties of coordination compounds. The examples are solved to illustrate concepts in coordination chemistry.

Uploaded by

Master Of Haking
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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2 8.

32 | Co-ordination Compounds

Solved Examples

JEE Main/Boards (E) Hexaaquamanganese (II) ion.

Example 1: Which of the following will give white Example 5: Write the correct formula for the following
precipitate with AgNO3 solution? coordination compounds:
(A) [Co (py)2 (H2O)2Cl2]Cl (A) CrCl3·6H2O (violet, with 3 chloride ions/unit formula)
(B) [Co (py)2H2OCl3]H2O (B) CrCl3·6H2O (light green, with 2 chloride ions/unit
formula)
Sol: (a) will give white precipitate (C) CrCl3·6H2O (dark green, with I chloride ion/unit
[Co (py)2 (H2O)2Cl2] Cl Co (py)2 (H2O)2Cl2] +Cl
+ – formula)

AgNO3 + Cl –
AgCl + NO–3 Sol: (A) [Cr (H2O)6] Cl3
(B) [CrCl (H2O)5] Cl2·H2O
Example 2: Specify the oxidation numbers of the metals
in the following coordination entities: (C) [CrCl2 (H2O)4] Cl·2H2O]

(A) [Co (CN) (H2O) (en)2]2+


(B) [PtCl4]2– Example 6: Draw the structure of:
(C) [CrCl3 (NH3)3] (A) Cis-dichlorotetracyanochromate (III) ion.
(D) [CoBr2 (en)2] + (d) K3 [Fe (CN)6] (B) Mer-triamminetrichlorocobalt (III).
(C) Fac –triaquatrinitrito-N-cobalt (III).
Sol: (A) +3, (B) +2, (C) +3, (D) +3, (E) +3]
Sol: 3-
Example 3: Using IUPAC rules, write the formula for the CN
following: (A)
NC Cl

(A) Tetrahydroxozincate (II) ion Cr


(B) Hexaamminecobalt (III) sulphate NC Cl
(C) Potassium tetrachloropalladate (II) CN
(D) Potassium tri (oxalato) chromate (III)
(E) Diamminedichloroplatinum (II) NH3
H3N Cl
Sol: (A) [Zn (OH)4]2–
(B)
(B) [Co (NH3)6]2 (SO4)3 (C) K2 [PdCl4] Co
(D) K3 [Cr (C2O4)3] (E) [PtCl2 (NH3)2] Cl Cl
NH3
Example 4: Using IUPAC norms write the systematic
names of the following:
(A) [Co (NH3)6]Cl3 (B) [CoCl(NO2) (NH3) 4]Cl H2O
(C) [Ni (NH3)6]Cl2 (D) [PtCl (NH2CH3) (NH3)2]Cl (C) O2N H2O
(E) [Mn (H2O) 6] 2+
Co
Sol: (A) Hexaamminecobalt (III) chloride. O2N H2O
(B) Tetraamminechloronitrito-N-cobalt (III) chloride. NH3
(C) Hexaamminenickel (II) chloride.
(D) Diamminechloro (methylamine) platinum (II) chloride. Example 7: Name the type of isomerism exhibited by
Chem i str y | 28.33

the following isomers: JEE Advanced/Boards


(A) [Cr(NH3)6] [Cr(CN)6] and [Cr(NH3)4(CN)2] [Cr(NH3)2(CN)4]
Example 1: What is the coordination number of the
(B) [Co(py)2 (H2O)3Cl]Cl2 and [Co(py)2 (H2O)2Cl2] Cl·H2O
central metal ions in the following complexes?
(C) [Pt (NH3)4Br2] Cl2 and [Pt (NH3)4Cl2] Br2
(A) [Cu (NH3)4]2+ (B) [Fe (C2O4)3]3–
(D) [Co (NH3)5NO2] Cl2 and [Co (NH3)5ONO] Cl2
(C) [Pt (en)2Cl2] (D) [Mo (CN)8]4–
Sol: (A) Coordination isomerism (B) Hydrate isomerism (E) [Fe (EDTA)]– (F) [Pd (H2O)2 (ONO)2I2]
(C) Ionization isomerism (D) Linkage isomerism
Sol: (A) NH3 is a monodentate ligand, Coordination
number of Cu2+ = 4 × no. of electron pairs accepted =
Example 8: Draw the structure of geometrical isomers 4 × 1 = 4.
of [Pt (gly)2] where gly is NH2CH2COO–. 2−
(B) C2 O 4 is a bidentate ligand, coordination number of
CH2 NH2 CH2
NH2 CH Fe3+ = 3 × 2 = 6.
Sol:CH2 NH2 NH2 2

PtPt (C) ‘en’ is a bidentate ligand and Cl– is a monodentate


OC ligand, coordination number of
OC OO OO OC
OC
cis-isomer
cis-isomer (D) Mo4+ = 8 × 1 = 8.

and and (E) EDTA is a hexadentate ligand, coordination number


and
of Fe3+ = 6 × 1 = 6.
CH2 2
CH NH
NH OO OC
OC
(F) H2O, ONO and I2 are monodentate ligands,
2 2

PtPt
coordination number of Pd4+ = 2 × 1 + 2 × 1 + 2 × 1 = 6.
OC
OC OO HH2N C C
2N

trans-isomer
trans-isomer
Example 2: A solution containing 2.665 g of CrCl3·6H2O
Example 9: [Cr(NH3)6] is paramagnetic while [Ni(CN)4]
3+ 2– is passed through a cation exchanger. The chloride
is diamagnetic. Why? ions obtained in solution were treated with excess of
AgNO3 to give 2.87 g of AgCl. Deduce the structure of
Sol: Electronic structure of the two complexes may be compound.
written as
Sol: Moles of Cl– ions ionized from moles of CrCl3·6H2O
[Ni (CN) 4]2–:
dsp
2
2.665
= = 0.01 Mol. Wt. of CrCl3·6H2O = 266.5
2.665
3d 4s 4p

CN CN CN CN
∴ Moles of AgCl obtained = Moles of Cl– ionized
In [Cr(NH3)6]3+, all the electrons are paired and hence it 2.87
is diamagnetic. = = 0.02
2
143.5
dsp

Thus, 0.01 mole of complex CrCl3·6H2O gives 0.02 moles


3d 4s 4p

of Cl– on ionization.
NH3 NH3 NH3 NH3 NH3 NH3
Now, since the coordination number of Cr is 6 and
Due to presence of three unpaired electrons in only one Cl ion is attached to Cr by coordination bond
[Ni(CN)4]2–, it is paramagnetic.] or secondary valency, the compound is [CrCl· (H2O)5]
Cl2·H2O.
Example 10: [Cu(CN)4]2– is more stable complex than [CrCl·(H2O)5]Cl2·H2O [CrCl·(H2O)5]2+ + 2Cl– + H2O
[Cu(NH3)4]2+. Why?
2Cl– + 2AgNO3 2AgCl + 2NO–3
Sol: The higher stability constant K = 2× 10 for Cu 27 2+

+ 4CN– → [Cu (CN)4]2– than for [Cu(NH3)4]2+ (which is Example 3: Two compounds have empirical formula
4.5 × 1011) explains stability. Also CN– is stronger ligand corresponding to Cr(NH3)3(NO2)3. In aqueous solution,
than NH3.] one of these is a non-electrolyte while the other conducts
electricity. What is the lowest possible formula weight of
2 8. 34 | Co-ordination Compounds

the conducting reagent? What is the highest possible Example 7: The magnetic moment of [MnCl4]2– is
formula weight for the non-conducting reagent? 5.92 B.M. On the basis of its magnetic moment, write
configuration of Mn2+ in this complex.
Sol: For complex Cr (NH3)3· (NO2)3 (H2O)2, the two
structures can be written as: Sol: For an atom/ion

Cr (NO2 ) · (NH3 ) · (H2 O ) ·NO2 ·H2 O Magnetic moment (µ) = n(n + 2)
 2 3  and (n = No. of unpaired electrons)
A
Given that µ = 5.92 B.M.
Cr (NO2 ) · (NH3 ) ·2 H2 O
 3 3 ∴ 5.92 = n(n + 2) n=5
B
Thus is this complex Mn contains 5 unpaired electrons
A will be a conducting reagent as it will give two ions on and so its possible configuration may be
dissolving in water. B will be a non-conducting reagent
Mn2+ in [MnCl4]2– = [Ar] 3d54s0
as it will not be ionized in water.
So hybridization of Mn2+ in the given complex must be sp3.
Example 4: Write the IUPAC name of the compound 3d
5
4s 4p
[Cr(NH3)5(NCS)][ZnCl4]. Is this compound colored? Mn2+:
sp3 hybridization
Sol: Pentammineisothicyanatochromium (III)
tetrachlorozincate (II). Compound will be colored
because Cr (III) has d3 configuration and so d–d Example 8: [Ni (CN)4]2– is diamagnetic while [NiCl4]2– is
transition is possible. paramagnetic, Why?

Sol: In [Ni (CN)4]2– all orbitals are doubly occupied,


Example 5: On the basis of valence bond theory explain hence it is diamagnetic whereas in [NiCl4)]2–, two orbitals
geometry, nature of hybridization, magnetic property are singly occupied, hence it is paramagnetic in nature.
and optical isomerism in:
(i) [Co (Ox)3]3– (ii) [CoF6]3– [NiCl4]2–:
Rearrangement
Sol: (i) [Co (Ox)3]3– i.e., trioxalato cobaltate (III) ion has 3
sp hybridization
sp3d2 hybridization, having octahedral geometry and
is paramagnetic in nature due to the presence of 4 Strong field ligands like CN–, CO, en, NO–2 have very
unpaired electrons. It has 2 optical isomers. strong electron donating tendency, hence electrons of
central metal ion pair up against Hund’s rule (low spin
(ii) [CoF6]3– i.e., Hexafluoro cobaltate (III) ion has sp3d2 complex). In [Ni (CO)4], Ni is sp3 hybridized with no
hybridization, having octahedral geometry and is unpaired electron, and hence it is diamagnetic.
paramagnetic in nature due to the presence of 4
unpaired electron. It does not show optical isomerism.
Example 9: What is the coordination entity formed
when excess of KCN is added to an aqueous solution
Example 6: The EAN of each Mn (Z = 25) in Mn2 (CO)10 of CuSO4? Why is that no precipitate of CuS is obtained
is 36. What is the structure of this complex? when H2S(g) is passed through this solution?

Sol: EAN = 25 (electrons from Mn atom) + 10 (electrons Sol: CuSO4 + 4KCN K2[Cu(CN)4] + K2SO4
from five CO ligand) + 1 (electron from Mn—Mn bond)
[Cu (CN)4]2– is stable complex having
= 36
Thus, structure will be, K = 2 × 1027 and so it does not provide sufficient Cu2+
CO CO CO CO
ion to give precipitate of CuS.
OC OC
Mn Mn Example 10: What do you understand by macrocyclic
CO CO CO CO
effect?

Sol: It is the increased thermodynamic stability of a


complex formed with a cyclic polydentate ligand when
compared to the complex formed with a noncyclic ligand,
Chem i str y | 28.35

e.g. Zn2+ complex with (I) is more stable than with (II).

NH NH NH NH
is
NH NH NH2 NH2

(II) Non-cyclic
(I) Cyclic

JEE Main/Boards

Exercise 1 Q.8 [Cr (NH3)6]3+ is paramagnetic while [Ni (CN)4]2– is


diamagnetic. Explain why?
Q.1 Explain the bonding in coordination compounds in Q.9 A solution of [Ni (H2O)6]2+ is green but a solution of
terms of Werner’s postulates. [Ni (CN)4]2– is colorless. Explain.

Q.2 FeSO4 solution mixed with (NH4) 2SO4 solution in 1:


Q.10 [Fe (CN)6]4– and [Fe (H2O)6]2+ are of different colors
1 molar ratio gives the test of Fe2+ ion but CuSO4 solution in dilute solutions. Why?
mixed with aqueous ammonia in 1: 4 molar ratio does
not give the test of Cu2+ ion. Explain why?
Q.11 Give the oxidation state, d orbital occupation and
coordination number of the central metal ion in the
Q.3 How many geometrical isomers are possible in the
following complexes:
following coordination entities?
(i) K3 [Co (C2O4)3] (ii) (NH4)2 [CoF4]
(i) [Cr (C2O4)3]3– (ii) [PtCl2 (en)2]2+
(iii) cis- [Cr (en)2Cl2] Cl (iv) [Mn (H2O)6] SO4
(iii) [Cr (NH3)2Cl2 (en)]

Q.12 Write down the IUPAC name for each of the


Q.4 Draw the structures of optical isomer of:
following complexes and indicate the oxidation state,
(i) [Cr (C2O4)3]3– (ii) [PtCl2 (en)2]2+ electronic configuration and coordination number. Also
(iii) [Cr (NH3)2Cl2 (en)] give stereochemistry and magnetic moment of the
complex:

Q.5 Draw all the isomers (geometrical and optical) of: (i) K [Cr (H2O)2 (C2O4)2].3H2O

(i) [CoCl2 (en)2]+ (ii) [Co (NH3) Cl (en)2]2+ (ii) [Co (NH3)4Cl] Cl2

(iii) [Co (NH3)2Cl2 (en)] (iii) CrCl3 (py)3


(iv) Cs [FeCl4]
Q.6 Aqueous copper sulphate solution (blue in color)
(v) K4 [Mn (CN)6]
gives:
(i) A green precipitate with aqueous potassium fluoride and
Q.13 What is meant by the chelate effect? Give an
(ii) A bright green solution with aqueous potassium example.
chloride. Explain these experimental results.
Q.7 What is the coordination entity formed when excess of Q.14 Amongst the following ions which one has the
aqueous KCN is added to an aqueous solution of copper highest magnetic moment value?
sulphate? Why is it that no precipitate of copper sulphide
(i) [Cr (H2O6)]3+ (ii) [Fe (H2O)6]2+
is obtained when H2S (g) is passed through this solution?
(iii) [Zn (H2O)6]2+
2 8. 36 | Co-ordination Compounds

Q.15 What will be the correct order for the wavelengths Q.7 Which type do d-electron configuration exhibit
of absorption in the visible region for the following? both low and high spin in octahedral complexes?
[Ni (NO2)6]4–, [Ni (NH3)6]2+, [Ni (H2O)6]2+? (A) d1 (B) d4 (C) d3 (D) d2

Q.16 Why NH4+ ion does not form complexes? Q.8 Transition elements have the maximum tendency to
form complexes because
Q.17 Write the formula of the following Complex. (A) They are metals and all metal form complexes
Pentaamminechlorocobalt (III) ion (B) They contain incompletely filled d-orbitals
(C) Their charge/size ratio is quite large
Exercise 2 (D) Both (B) and (C)
Q.9 [(H2 O)5 Co – O – O – Co(H2 O)5 ]4 +
Single Correct Choice Type ( A)


Q.1 Which of the following compound is not having
[(H2 O)5 Co – O – O – Co(H2 O)5 ]5 +
synergic bonding? (B)

(A) Fe (CO)5 (B) [Ni (CN)4] 2–

What will be the bond length of O–O in complex A and B?


(C) [Fe (π–C5H5)2] (D) [CoF6]3–
(A) A = B (B) A > B (C) B > A (D) None
Q.2 Which of the following is a low spin complex?
Q.10 In the complex of [Ma3b3]n±, if two ‘a’ are replaced
(A) Ni (CO)4 (B) [Ni (NH3)6]2+
by AA type of ligand, then isomer of it, only one isomer
(C) [Cu (NH3)4]2+ (D) All of these of the product will be formed.
(A) Only Fac-isomer
Q.3 Which of the following name is incorrect for the
(B) Only Mer-isomer
given complex. K [Fe(H2O)2(NCS)3(NO3)]
(C) Fac and Mer-isomer both
(A) Potassium diaquatrisothiocyanatonitrato ferrate (III)
(D) None of these
(B) Potassium diaquanitratotrithiocyanato-N- ferrate (III)
(C) Potassium diaquatrithiocyanato-N-nitrito ferrate (III)
Q.11 What is the hybridization of Fe in sodium
(D) Potassium diaquatrisothiocyanatonitrato ferrate (II) thionitroprusside?
(A) sp3d2 (B) d2sp3
Q.4 What is the hybridization of Fe in [Fe (CO) 4]?
(C) sp3d (D) No hybridization
(A) sp3 (B) dsp2 (C) sp (D) sp3d2

Q.12 What is correct name of linkage isomer of [Cr (H2O)5


Q.5 Which of the following complex/molecule acts as a (NO2)] Br2.
reducing agent?
(A) Pentaaquanitro-‘O’ chromium (III) bromide
(A) [Co(NH3)6]2+ (B) [Mn (CO)6]
(B) Pentaaquanitro chromium (III) bromide
(C) NO (D) All are acts as a Reducing
(C) Pentaaquonitro chromium (III) bromide
(D) Pentaaquanitrito-‘O’’ chromium (II) bromide
Q.6 Which of the following molecule is square planar.
(A) K4 [Ni (CN)4] (B) [Be (acac)2] Q.13 The effective atomic number of Co (CO)4 is 35. It
does not attain stability by
O
(C) B (D) Pd (NH3 )(H2 O )(Br ) Cl º (A) Oxidation of [Co (CO)4]
O 2
(B) Reduction of [Co (CO)4]
(C) Dimerization of [Co (CO)4]
(D) By both (B) and (C)
Chem i str y | 28.37

Q.14 Which one of the following ions is colored? Previous Years’ Questions
(A) Sc3+ (B) Ti4+ (C) Zn2+ (D) V2+
Q.1 The coordination number of a central metal atom in
a complex is determined by  (2004)
Q.15 Which of the following statement is correct.
(A) The number of ligands around a metal ion bonded
(A) The name of [Fe (H2O)5NO] SO4 is
by sigma and pi-bonds both.
pentaaquanitrosyliron (II) sulphate
(B) The number around a metal ion bonded by pi-bonds
(B) [Co(C2O4)3]3– does not have any unpaired electron
(C) The number of ligands around a metal ion bonded
(C) E.A.N. of [Fe (CO)2(NO)2] is 34 by sigma bonds
(D) [SnCl3]– acts as ligand where the Cl-atom as donor (D) The number of only anionic ligands bonded to the
atom. metal ion
Q.16 How many stereoisomer are possible for complex Q.2 Among the properties (i) reducing (ii) oxidizing (iii)
[Co(NH3)3Cl3] complexing, the set of properties shown by CN– ion
(A) 1 (B) 2 (C) 3 (D) 4 towards metal species is  (2004)
(A) iii, i (B) ii, iii (C) i, ii (D) i, ii, iii
Q.17 In the volumetric analysis, Mohr’s salts is preferred
to ferrous sulphate because Q.3 Ammonia forms the complex ion [Cu (NH3)4]2+
(A) It is more readily oxidizable than FeSO4 with copper ions in alkaline solutions but not in acidic
solution. What is the reason for it?  (2003)
(B) It is less easily oxidizable than FeSO4
(C) It can undergo both oxidation and reduction (A) In acidic solutions hydration protects copper ions
(D) It can be oxidized even in the absence of dilute H2SO4. (B) In acidic solutions protons coordinate with ammonia
molecules forming NH4+ ions and NH3 molecules are
not available
Q.18 [RhF6]5– complex ion is a
(C) In alkaline solutions insoluble Cu(OH)2 is precipitated
(A) Outer orbital complex which is soluble in excess of any alkali
(B) Inner orbital complex (D) Copper hydroxide is an amphoteric substance
(C) No outer or no inner orbital complex
(D) None of these Q.4 In the coordination compound, K4[Ni(CN)4] oxidation
state of nickel is  (2003)
Q.19 Which of the following complex are tetrahedral in (A) –1 (B) 0 (C) +1 (D) +2
shape.
(A) [FeCl4]– (B) [BrF4]– Q.5 The coordination number and the oxidation state of
(C) [Cu(CN)4]3– (D) [AuCl4]– the element ‘E’ in the complex [E(en)2(C2O4)]NO2 (where
(en) is ethylene diamine) are, respectively  (2008)
Q.20 How many ions are produced from the complex (A) 4 and 2 (B) 4 and 3
Co (NH3)6Cl2 in solution? (C) 6 and 3 (D) 6 and 2
(A) 6 (B) 4 (C) 3 (D) 2
Q.6 Which among the following will be named as
Q.21 The oxidation number of cobalt in K [Co (CO)4] is dibromidobis (ethylene diamine) chromium (III)
bromide  (2012)
(A) +1 (B) +3 (C) –1 (D) –3
(A) [Cr (en)3] Br3 (B) [Cr (en)2Br2] Br
Q.22 Amongst the following the most stable complex is (C) [Cr (en) Br4]– (D) [Cr (en)Br2] Br
(A) [Fe (H2O6)]3+ (B) [Fe (NH3)6]3+
(C) [Fe (C2O4)3]3– (D) [FeCl6]3–
2 8. 38 | Co-ordination Compounds

Q.7 The “spin-only” magnetic moment [in units of Bohr Q.15 In Fe (CO)5, the Fe-C bond possesses (2006)
magneton, (µB)] of Ni2+ in aqueous solution would be
(A) π-character only (B) Both σ and π characters
(At. No. Ni = 28)  (2006)
(C) Ionic character (D) σ-character only
(A) 2.83 (B) 4.90 (C) 0 (D) 1.73

Q.16 The coordination number and the oxidation state


Q.8 The pair in which both species have same magnetic
moment (spin only value) is  (2006) of the element ‘E’ in the complex E ( en) ( C2O 4 )  NO2
 2 
(A) [Cr (H2O)6]2+, [CoCl4]2– (B) [Cr (H2O)6]2+, [Fe (H2O)6]2+ (where (en) is ethylene diamine) are respectively, (2008)

(C) [Mn (H2O6)]2+, [Cr (H2O)6]2+ (D) [CoCl4]2–, [Fe (H2O)6]2+ (A) 6 and 2 (B) 4 and 2
(C) 4 and 3 (D) 6 and 3
Q.9 Which of the following has an optical isomer? (2009)
(A) [Co (NH3)3Cl]+ (B) [Co (en) (NH3)2]2+ Q.17 Being lesser energy difference between 5f and
6d than 4f and 5d orbitals. In which of the following
(C) [Co (H2O)4 (en)]3+ (D) [Co (en)2 (NH3)2]3+ octahedral complexes of Co (at no. 27), will the
magnitude of be the highest? (2008)
Q.10 Which of the following pairs represents linkage
3− 3−
isomers ?  (2009) (A) Co ( CN)  (B) Co ( C2O 4 ) 
 6  3
(A) [Cu (NH3)4] [PtCl4] and [Pt (NH3)4] [CuCl4]
3+ 3+
(B) [Pd (P Ph3)2 (NCS)2] and [Pd (P Ph3)2(SCN)2] (C) Co (H2O )  (D) Co (NH3 ) 
 6  6

(C) [Co(NH3)5NO3]SO4 and [Co (NH3)5SO4]NO3


(D) [PtCl2 (NH3)4] Br2 and [Pt Br2 (NH3)4] Cl2 Q.18 Which of the following has an optical isomer?
(2009)

Q.11 Which one of the following has a square planner + 2+


(A) Co (NH3 ) Cl (B) Co ( en)(NH3 ) Cl
geometry?  (2007)  3   2 

(A) [CoCl4]2– (B) [FeCl4]2– (C) [NiCl4]2– (D) [PtCl4]2– 3+ 3+


(C) Co (H3O ) ( en)  (D) Co ( en) (NH3 ) 
 4   2 2

Q.12 Which of the following facts about the complex


[Cr (NH3)6] Cl3 is wrong  (2011) Q.19 Which of the following pairs represents linkage
isomers? (2009)
(A) The complex involves d2sp3 hybridization and is
octahedral in shape
 ( 4  )
(A)  Cu (NH3 )  PtlCl4  and Pt (NH3 )  CuCl4 
(B) The complex is paramagnetic
(C) The complex is an outer orbital complex (B) Pd (PPh3 )(NCS )  and Pd (P Ph2 ) ( SCN2 ) 
 2  2 
(D) The complex gives white precipitate with silver nitrate
solution (C) Co (NH3 ) NO3  SO 4 and Co (NH3 ) SO 4  NO3
 5   5 

(D) PtCl2 (NH3 )  Be2 and PtBr2 (NH3 )  Cl2


Q.13 One mole of the complex compound Co (NH3)5Cl3,  4  4
gives 3 moles of ions on dissolution in water. One mole
of the same complex reacts with two moles of AgNO3 Q.20 A solution containing 2.675 g of CoCl3.6 NH3
solution to yield two moles of AgCl (s). The structure of (molar mass = 267.5 g mol-1) is passed through a cation
the complex is  (2003) exchanger. The chloride ions obtained in solution were
treated with excess of AgNO3 to give 4.78 g of AgCl
(A) [Co (NH3)5Cl] Cl2 (B) [Co (NH3)3Cl3].2NH3
(molar mass = 143.5 g mol‒1). The formula of the complex
(C) [Co (NH3)4Cl2] Cl.NH3 (D) [Co (NH3)4Cl] Cl2.NH3 is (At. Mass of Ag = 108 u) (2010)

(A) Co ( NH3 )6  Cl3 (B) CoCl2 ( NH3 )4  Cl


Q.14 How many EDTA (ethylenediaminetetraacetic acid)
molecules are required to make an octahedral complex
with a Ca2+ion  (2006) (C) CoCl3 ( NH3 )3  (D) CoCl ( NH3 )5  Cl2
(A) Six (B) Three (C) One (D) Two
Chem i str y | 28.39

Q.21 Which one of the following has an optical Q.26 The octahedral complex of a metal ion M3+ with
isomer? (2010) four monodentate ligands L1, L2, L3 and L4 absorb
2+ wavelengths in the region of red, green, yellow and blue,
(A)  Zn ( en ) ( NH3 )2  (B) [Co ( en )3 ]3+ respectively. The increasing order of ligand strength of
the four ligands is (2014)
3+
(C) Co ( H2O )4 ( en )  (D) [ Zn ( en )2 ]2+ (A) L4 < L3 < L2 < L1 (B) L1 < L3 < L2 < L4
(C) L3 < L2 < L4 < L1 (D) L1 < L2 < L3 < L4

Q.22 Which of the following facts about the complex Q.27 The number of geometric isomers that can exist
Cr (NH )  Cl wrong? (2011)
for square planar Pt ( Cl)(py )(NH3 )(NH2OH)  is
+
 3 6 3
 
(A) The complex is paramagnetic (py = pyridine): (2015)
(B) The complex is an outer orbital complex (A) 2 (B) 3 (C) 4 (D) 6
(C) The complex gives white precipitate with silver
nitrate solution Q.28 Which of the following compounds is not colored
(D) The complex involves d sp hybridization and is
2 3 yellow? (2015)
octahedral in shape.
(A) Zn2 Fe ( CN)  (B) K 3 Co (NO2 ) 
 6  6

(C) (NH4 )3  As (Mo3O10 ) 4 


2−
Q.23 The magnetic moment (spin only) of NiCl4  is (D) BaCrO 4
(2011)
(A) 5.46 BM (B) 2.83 BM (C) 1.41 BM (D) 1.82 BM
Q.29 The pair having the same magnetic moment is:
[At. No.: Cr = 24, Mn = 25, Fe = 26, Co = 27] (2016)
Q.24 Which among the following will be named
as dibromidobis (ethylene diamine) chromium (III) 2+ 2+
(A) Cr (H2O )  and Fe (H2O ) 
bromide? (2012)  6  6

2+
(B) Mn (H2O ) 
2+
(A) Cr ( en)  Br3
 3  ( )
(B) Cr en Br2  Br
2   6
and Cr (H2O ) 
 6

2+
(C) Cr ( en) Br4  ( )

and Fe (H2O ) 
2−
(D) Cr en Br2  Br (C) CoCl4 
   6
Q.25 Which of the following complex species in not 2+
(D) Cr (H2O ) 
2−
expected to exhibit option isomerism? (2013) and CoCl4 
 6

3+ +
(A) Co ( en)3  (B) Co ( en)2 Cl2  Q.30 Which one of the following complexes shows
optical isomerism? (2016)
+
(C) Co (NH3 )3 Cl3  (D) Co ( en)2 (NH3 )2 Cl2  (A) cis Co ( en) Cl2  Cl (B) trans Co ( en)2 Cl2  Cl
 2 
(C) Co (NH3 ) 4 Cl2  Cl (D) Co (NH3 )3 Cl3 
2 8. 40 | Co-ordination Compounds

JEE Advanced/Boards

Exercise 1 Q.11 Square planar complexes with co-ordination


number four exhibit geometrical isomerism whereas
Q.1 Explain with two examples each of the following: tetrahedral complexes does not. Why?
coordination entity, ligand, coordination number,
coordination polyhedron, homoleptic and heteroleptic. Q.12 Determine the oxidation state of metal in the
complex ion, [PtCl6]2–?
Q.2 What is meant by unidentate, bidentate and
ambidentate ligands? Give two examples for each. Q.13 The color of Hg2Cl2 changes from white to black
when treated with NH3. Why?
Q.3 (A) What is the basis of formation of spectrochemical
series? Q.14 [Fe (CN)6]3– is weakly paramagnetic while [Fe(CN)6]4–
(B) Draw the structure of geometrical isomers of the is diamagnetic, why?
following coordination complexes: [Co(NH3)3Cl3] and
[CoCl2 (en)2]+ Q.15 The magnetic moment of [MnCl4]2– is 5.92 B.M. On
the basic of its magnetic moment, write configuration of
Q.4 Write all the geometrical isomers of [Pt (NH3) (Br) Mn2+ in this complex.
(Cl) (py)] and how many of these will exhibit optical
isomers? Q.16 List various types of isomerism possible for
coordination compounds, giving an example of each.
Q.5 What is meant by stability of a coordination Q.17 Discuss the nature of bonding in the following
compound in solution? State the factors which govern coordination entities on the basis of valence bond
stability of complexes. theory.
(A) [Fe (CN)6]4– (B) [FeF6]3–
Q.6 Draw a sketch to show the splitting of d-orbitals
in an octahedral crystal filed. State for a d5 ion how (C) [Co (C2O4)3]3– (D) [CoF6]3–
the actual configuration of the split d-orbitals in an
octahedral crystal field is decided by the relative values Q.18 Draw figure to show the splitting of d orbital in an
of D and P. octahedral crystal field.

Q.7 Writ the IUPAC name of [Co (en)2Cl2] Cl and draw Q.19 What is spectrochemical series? Explain the
the structures of all the isomers with this formula of difference between a weak field ligand and a strong
complex. field ligand.

Q.8 Draw diagram to show crystal field splitting in a Q.20 What is crystal field splitting energy? How does
tetrahedral crystal field the magnitude of ∆o decide the actual configuration of
d orbital in a coordination entity?

Q.9 Discuss briefly giving an example in each case the


Q.21 Discuss the nature of bonding in metal carbonyls.
role of coordination compounds in:
Q.22 Specify the oxidation numbers of the metals in the
(i) Biological systems
following coordination entities and geometry of these
(ii) Medicinal chemistry compound?
(iii) Analytical chemistry and
(i) [Co (H2O) (CN) (en)2]2+ (ii) [CoBr2(en)2]+
(iv) Extraction/metallurgy of metals.
(iii) [PtCl4]2– (iv) K3 [Fe (CN)6]
(v) [Cr (NH3)3Cl3]
Q.10 NH2.NH2 although possesses two electron pair for
donation but not acts as chelating agent. Why?
Chem i str y | 28.41

Q.23 Using IUPAC norms write the formulas for the


following and explain all property according to VBT? Q.4 The effective atomic number of Co(CO)4 is 35. It
(1) Tetrahydroxozincate (II) does not attain stability by
(2) Potassium tetrachloridopalladate(II) (A) Oxidation of [Co(CO)4] (B) Reduction of [Co(CO)4]
(3) Diamminedichloridoplatinum (II) (C) Dimerization of [Co(CO)4] (D) By both (B) and (C)
(4) Potassium tetracyanonickelate (II)
(5) Pentaamminenitrito-O-cobalt (III) Q.5 In the volumetric analysis, Mohr’s salt is preferred to
(6) Hexaamminecobalt (III) sulphate ferrous sulphate because
(7) Potassium tri (oxalate) chromate (III) (A) It is more readily oxidizable than FeSO4
(8) Hexaammineplatinum (IV) (B) It is less easily oxidizable than FeSO4
(9) Tetrabromideocuprate (II) (C) It can undergo both oxidation and reduction
(10) Pentaamminenitrito-N-cobalt (III) (D) It can be oxidized even in the absence of dilute H2SO4

Q.24 Write the difference between VBT and CFT?


Multiple Correct Choice Type

Q.25 Write the formulas for the following coordination Q.6 Select the correct statement.
compounds:
(A) CO bond order in bridging carbonyl group is found
(i) Tetraaminequachloridocobalt (III) chloride to be lower than in that terminal carbonyl group in
(ii) Potassium tetrahydroxozincate (II) Fe2(CO)9.
(iii) Potassium trioxalatoaluminate (III) (B) Bond angle in NO2 < Bond angle in NO2–
(iv) Dichloridobis (ethane-1, 2-diamine) cobalt (III) (C) CO is a σ donor as well as π acceptor ligand.
(v) Tetracrabonylnickel (0). (D) NO is the only σ donor ligand.

Exercise 2 Q.7 Which of the following complex is/are square planar


as well as paramagnetic?
Single Correct Choice Type (A) [AuCl4]– (B) [CuCl4]–

Q.1 Select the correct order of C—O bond order in (C) [Cu (NH3)4]2+ (D) [Co (dmg)2]º
following complexes.
(A) [M (CO3(PCl3)2(PMe3)] > [M(CO)3(PCl3)3] > [M(CO)3(PCl3) Q.8 Which one of the following statements is incorrect
(PMe3)2] about transition elements?
(B) [M(CO)3(PCl3)2(PMe3)2] > [M(CO)3(PCl3)3] > [M(CO)3 (A) The last electron enters in the d-orbital
(PCl3)2(PMe3)]
(B) Their properties are in between those of s-block
(C) [M(CO)3(PCl3)(PMe3)2] = [M(CO)3(PCl3)3] < [M(CO)3 elements and p-block elements
(PCl3)2(PMe3)] (C) The transition element with smallest atomic number
(D) [M (CO)3(PCl3)3] > [M(CO3(PCl3)2(PMe3)] > [M(CO)3 is scandium
(PCl3)(PMe3)2] (D) Lanthanum is not a transition element but is a
lanthanide.

Q.2 What is the hybridization of Fe in [Fe (CO)4]?


Q.9 Which of the following type of complex (s) is/are
(A) sp3 (B) dsp2 (C) sp (D) sp3d2 having six number of stereoisomers.
(A) [MA2B2C2]n± (B) [M (AB) A2BC]n±
Q.3 Which of the following complex/molecule acts as a
reducing agent. (C) [M (AA) A2B2]n± (D) [M (AB) A2B2]n±

(A) [Co(NH3)6]2+ (B) [Mn(CO)6]


(C) NO (D) All act as a reducing agent
2 8. 42 | Co-ordination Compounds

Q.10 Which of the following complex (s) is/are low spin Q.17 Which of the following ligand can show linkage
isomerism?
(A) K4 [Fe (CN)6] (B) [PtCl4]2–
(C) [Co (C2O4)3]
3–
(D) [Ni (NH3)6]2+ (A) NMe3 (B) O CN (C) SO42– (D) None of these

Q.11 Which of the following molecules have same Q.18 Which of the following ligand can show linkages
number of unpaired electrons. isomerism?
(A) [Cu (NH3)6]2+ (B) [Ti (H2O)6]3+ (A) It increase the stability of complex.
(C) K4 [Fe (CN)6O2] (D) [Cr (NH3)6]3+ (B) It increase the strength of metal–ligand bond.
(C) More negative charge on the central atom causes
Q.12 Which of the following type of complex (s) do/ more extent of synergic bonding.
does not produce optically active isomer (s). (D) All of these
(A) MA2B2C2 (B) MA4B2
(C) MA3B2C (D) MA2B2CD Q.19 Choose the incorrect statement from the following
options.

Q.13 For which of the complex, the E.A.N. of the central (A) C2H2 can acts as π-acid ligand
atom of the complex obeys Sidgwick E.A.N. rule. (B) [MA3B2C]n±: All isomers are optically inactive.
(A) [Ti (σ–C5H5)5]2 (B) [Fe(NO)2(CO)2] (C) [MABCDE2]n± complex has total 12 optically active
isomer
(C) [Ag(CN)2]– (D)[Hg(SCN)4]2–
(D) All statements are incorrect.

Q.14 Identify the ligands can cause the linkage isomerism.


Paragraph 2: Metals from complexes with various lewis
(A) NO3– (B) NO2– (C) OCN– (D) S2O32– bases called ligands, more the basic character better is
the complex. Electron donating tendency decreases with
increase in electronegativity of donor atoms in a period.
Assertion Reasoning Type Higher the bond order of metal ligand bond more is
the stability of complex. Geometry and symmetry also
(A) Statement-I is true, statement-II is true and influence the stability of complex. More symmetricity of
statement-II is correct explanation for statement-I. the complex, more is the stability.
(B) Statement-I is true, statement-II is true and
statement-II is not the correct explanation for
Q.20 Little Mohr’s salt was dissolved in a water sample
statement-I.
containing CO32–, Cl–, CN– and OH– in minute amounts.
(C) Statement-I is true, statement-II is false. Fe2+ prefers formation of complex with
(D) Statement-I is false, statement-II is true.
(A) CO32– (B) Cl– (C) CN– (D) OH–

Q.15 Statement-I: [Cr(NH3)6]3+ has three unpaired


Q.21 Fe2+ forms diamagnetic complex with either of
electron in t2g orbital
CO32–, Cl–, CN– or OH–. Geometry of the complex formed
Statement-II: [Cr(NH3)6]3+ does not show geometrical is supposed to be
isomerism.
(A) Tetrahedral (B) Triangular bipyramidal
(C) Octahedral (D) Square planar
Q.16 Statement-I: The square planar complex, [Mabcd]n+
type shows geometrical isomerism.
Q.22 Least stable complex is
Statement-II: Restricted rotation around the single
(A) Mn (CO)5 (B) K [V (CO)5]
bond is present within the above complex.
(C) K [Fe (NC)6] 4–
(D) [Fe (NC)6]4–
Comprehension Type

Paragraph 1: Isomerism is a phenomenon where the


molecules are having same formula but they have
different structures.
Chem i str y | 28.43

Match the Columns Q.27

Q.23 Column I Column II


(A) [Pt (NH3)5Cl] Cl3 (p) 229
Column I Column II
(B) [Pt (NH3)4Cl2] Cl2 (q) 9
7
(A) Na [Co (CO)4] Pt (p) C
 omplex having only
monodentate ligand (C) [Pt (NH3)3Cl3] Cl (r) 404
(B) (Trien) Cl2 (q) C
 omplex not following Sidgwick
EAN rule. (D) [Pt (NH3)6] Cl3 (s) 523
(C) [Fe (H2O)5NO] SO4 (r) C
 omplex is having 3 or 5
member of ring within it.
(D) [Fe (EDTA)]– (s) Complex having positively Previous Years’ Questions
charged ligand
(t) Complex having chelating ligand Q.1 Amongst the following, the lowest degree of
paramagnetism per mole of the compound at 298 K will
be shown by (1988)
Q.24
(A) MnSO4·4H2O (B) CuSO4·5H2O
Column I Column II
(C) FeSO4·6H2O (D) NiSO4·6H2O
(A) [Co(CO)4]– (p) E.A.N ≠ 36

(B) [Zn(gly)2] (q) S


 ynergic bonding is involved Q.2 Which of the following is formed when excess of
KCN is added to aqueous solution of copper sulphate?
(C) [Ag(CN)2]– (r) T
 wo optically active isomer
(1996)
(s) The complex is diamagnetic (A) Cu(CN)2 (B) K2[Cu(CN)4]
(C) K[Cu(CN)2] (D) K3[Cu(CN)4]
Q.25
Q.3 The complex ion which has no ‘d’ –electrons in the
Column I Column II central metal atom is (2001)
(A) [M(AA)3] (p) T
 wo pair of enantiomer (A) [MnO4]– (B) [Co (NH3)6]3+
(B) [M(AB)B2C2] (q) F our geometrical isomer (C) [Fe (CN)6]3– (D) [Cr (H2O)6]3+
(C) [M(AB)3] (r) T
 wo optically inactive isomer
Q.4 The compound having tetrahedral geometry is
(D) [MA3BCD] (s) Two optically active isomer
(2004)
(t) A
 t least one stereoisomer is
planar
(A) [Ni(CN)4]2– (B) [Pd(CN)4]2– (C) [PdCl4]2– (D) [NiCl4]2–

Note: AA,AB, a, b, c, d are not having chiral center. Q.5 The IUPAC name of [Ni (NH3)4] [NiCl4] is (2008)
(A) Tetrachloronickel (II)-tetraamminenickel (II)
Q.26
(B) Tetraamminenickel (II)-tetrachloRonickel(II)
Column I Column II
(C) Tetraamminenickel (II)-tetrachloronickelate (II)
(A) Zn [Fe (CN)5NO] (p) Blue color due to charge transfer
(D) Tetrachloronickel (II)-tetraamminenickelate (0)
(B) [Fe (H2O)5NO] SO4 (q) d2sp3 hybridization

(C) Fe4 [Fe (CN)6]3 (r) P


 aramagnetic compound
Q.6 Geometrical shapes of the complexes formed by
the reaction of Ni2+ with Cl–, CN– and H2O, respectively,
(D) K4[Fe(CN)5O2] (s) NO acts as positive ligand are (2011)
(t) C
 harge transfer metal to metal in (A) Octahedral, tetrahedral and square planar
complex.
(B) Tetrahedral, square planar and octahedral
(C) Square planar, tetrahedral and octahedral
(D) Octahedral, square planar and octahedral
2 8. 44 | Co-ordination Compounds

Q. 7 Among the following metal carbonyls, the C—O Q.15 NiCl2 in the presence of dimethyl glyoxime (DMG)
bond order is lowest in (2007) gives a complex which precipitates in the presence of
NH4OH, giving a bright red color. (2004)
(A) [Mn(CO)6]+ (B) [Fe(CO)5] (C) [Cr(CO)6] (D) [V(CO)6]–
(A) Draw its structure and show H-bonding
Q.8 Statement-I: The geometrical isomers of the (B) Give oxidation state of Ni and its hybridization
complex [M(NH3)4Cl2] are optically inactive.
(C) Predict whether it is paramagnetic or diamagnetic
Statement-II: Both geometrical isomers of the complex
[M(NH3)4Cl2] possess axis of symmetry. (2008)
Q.16 Statement-I: Fe (H2O )5 NO  SO 4 is paramagnetic
(A) Statement-I is true, statement-II is true and
statement- II is correct explanation for statement-I. Statement-II: The Fe in Fe (H2O )5 NO  SO 4 has three
unpaired electrons. (2008)
(B) Statement-I is true, statement-II is true and
statement-II is not the correct explanation for (A) Statement-I is true, statement-II is true; statement-II
statement-I. is correct explanation for statement-I
(C) Statement-I is true, statement-II is false. (B) Statement-I is true, statement-II is true; statement-II
(D) Statement-I is false, statement-II is true is NOT a correct explanation for statement-I
(C) Statement-I is true, statement-II is false
Q.9 Match the Columns (2007) (D) Statement-I is false, statement-II is true

Match the complexes in column I with their properties


listed in column II. Q.17 As per IUPAC nomenclature, the name of the
complex is Co (H2O ) (NH3 ) Cl3  (2012)
Column-I Column-II
 4 2 

(A) [Co(NH3)4(H2O)2]Cl2 (p) G


 eometrical isomers (A) Tetraaquadiaminecobalt (III) chloride

(B) [Pt(NH3)2 Cl2] (q) Paramagnetic (B) Tetraaquadiamminecobalt (III) chloride


(C) Diaminetetraaquacobalt (III) chloride
(C) [Co(H2O)5Cl2] (r) Diamagnetic
(D) Diamminetetraaquacobalt (III) chloride
(D) [Ni(H2O)6]Cl2 (s) M
 etal ion with+2 oxidation state

Q.18 Consider the following complex ions, P, Q and R


Q.10 Total number of geometrical isomers for the
3− 2+ 2+
complex [RhCl (CO) (PPh3) (NH3)] is (2010)
= FeF6  ,Q  V (H2O ) =
P = and R Fe (H2O ) 
 6  6

The correct order of the complex ions, according to their


Q.11 The volume (in mL) of 0.1 M AgNO3 required for
spin–only magnetic moment values (in B.M.) is (2013)
complete precipitation of chloride ions present in 30 mL
of 0.01 M solution of [Cr (H2O)5Cl] Cl2, as silver chloride (A) R < Q < P (B) Q < R < P
is close to …… (C) R < P < Q (D) Q < P < R

Q.12 Identify the complexes which are expected to be


Q.19 The pair(s) of coordination complexes/ions
colored. Explain (1994)
exhibiting the same kind of isomerism is(are) (2013)
(i) [Ti (NO3)4] (ii) [Cu (NCCH3)] + BF4
(iii) [Cr (NH3)6] Cl3 (iv) K3 [VF6] (A) Cr (NH3 ) Cl Cl2 and Cr (NH3 ) Cl Cl
 5   4 
+ +
(B) Co (NH3 ) Cl2  and Pt (NH3 ) (H2O ) Cl
Q.13 Draw the structures of [Co (NH3)6]3+, [Ni (CN)4]2–  4   2 
and [Ni (CO)4]. Write the hybridization of atomic orbitals 2− 2−
of the transition metal in each case. (2000) (C) CoBr2Cl2  and PtBr2Cl2 

(D) Pt (NH3 ) (NO3 )  Cl and Pt (NH3 ) Cl Br


Q.14 Write the IUPAC name of the compound K2 [Cr (NO)  3   3 
(CN)4(NH3)]. Spin magnetic moment of the complex
µ = 1.73 BM. Give the structure of anion. (2003)
Chem i str y | 28.45

Q.20 Match the orbital overlap figures shown in list-I Q.22 Among the complex ions,
with the description given in list-II and select the correct + 3−
answer using the code given below the lists. (2014) Co (NH2 − CH2 − CH2 − NH2 ) Cl2  , Crl2 ( C2O 4 )  ,
   2
−.
( )
+
Fe (H O ) ( OH)  , Fe NH ( CN ) 
List-I List-II  2 4 2  3 4 
2+
(p) p − dπ anticoding Co (NH2 − CH2 − CH2 − NH2 ) Cl
 
(A) 2+
and Co (NH3 ) (H2O ) Cl2 
 4 
the number of complex ion(s) that show(s) cis-trans
(q) d − dσ  bonding isomerism is (2015)
(B)

Q.23 In the complex acetylbromidodicarbonylbis


(triethylphosphine) iron(II), the number of Fe–C bond(s)
(r) p − dπ bonding is (2015)
(C)
Q.24 Among [Ni(CO)4], [NiCl4]2‒, [Co(NH3)4 Cl2]Cl,
Na3[CoFe6], Na2O2 and CsO2 the total number of
(s) d − d σ paramagnetic is (2016)

(D) (A) 2 (B) 3 (C) 4 (D) 5

Q.25 The number of geometric isomers possible for the


Code: complex [CoL2Cl2]– (L = H2NCH2CH2O–) is (2016)

p Q r Ss
Q.26 The geometries of the ammonia complexes of
(A) 2 1 3 4
respectively, are (2016)
(B) 4 3 1 2
(C) 2 3 1 4 (A) Octahedral, square planar and tetrahedral
(D) 4 1 3 2 (B) Square planar, octahedral and tetrahedral

(C) Tetrahedral, square planar and octahedral


Q.21 For the octahedral complexes of Fe in SCN 3+ ‒
(D) Octahedral, tetrahedral and square planar
(thiocyanato-S) and in CN‒ ligand environments, the
difference between the spin-only magnetic moments
in Bohr magnetons (When approximated to the nearest
integer) is
[Atomic number of Fe = 26] (2015)
2 8. 46 | Co-ordination Compounds

MASTERJEE Essential Questions


JEE Main/Boards JEE Advanced/Boards

Exercise 1 Exercise 1

Q.2 Q.5 Q.12 Q.6 Q.13 Q.19


Q.23 (iii, v, vii, ix) Q.25

Exercise 2
Exercise 2
Q.6 Q.8 Q.13
Q.18 Q.22 Q.4 Q.11 Q.15
Q.18 Q.29

Previous Years' Questions


Previous Years' Questions
Q.2 Q.5 Q.8
Q.10 Q.11 Q.14 Q.1 Q.6 Q.12

Answer Key

JEE Main/Boards

Exercise 2

Single Correct Choice Type

Q.1 D Q.2 D Q.3 D Q.4 B Q.5 D Q.6 D Q.7 B

Q.8 D Q.9 B Q.10 C Q.11 B Q.12 A Q.13 B Q.14 D

Q.15 B Q.16 B Q.17 B Q.18 B Q.19 A Q.20 C Q.21 C

Q.22 C

Previous Years’ Questions

Q.1 C Q.2 A Q.3 B Q.4 B Q.5 C Q. 6 B Q.7 A


Q.8 B Q.9 D Q.10 B Q.11 D Q.12 C Q.13 A Q.14 C
Q.15 B Q.16 D Q.17 A Q.18 D Q.19 B Q.20 A Q.21 B
Q.22 B Q.23 B Q.24 B Q.25 C Q.26 B Q.27 B Q.28 A
Q.29 A Q.30 A
Chem i str y | 28.47

JEE Advanced/Boards
Exercise 2

Single Correct Choice Type

Q.1 D Q.2 B Q.3 D Q.4 A Q.5 B

Multiple Correct Choice Type

Q. 6 A, C Q.7 C, D Q.8 C, D Q.9 A, D Q.10 A, B, C Q.11 A, B, C


Q.12 A, B, C, D Q.13 A, C, D Q.14 B, C, D

Assertion Reasoning Type

Q.15 B Q.16 C

Comprehension Type

Paragraph 1: Q.17 B Q.18 D Q.19 C Paragraph 2: Q.20 C Q.21 C Q.22 B

Match the Colulmns

Q.23 A → p; B → q, r, t; C → p, q, s; D → q, r, t Q.24 A → q, s; B → r, s; C → p, q, s
Q.25 A → s; B → p, q, r; C → p; D → q, s Q.26 A → q, s; B → r, s; C → p, q, r, t; D → q, r
Q.27 A → r; B → p; C → q; D → s

Previous Years’ Questions

Q.1 B Q.2 D Q.3 A Q.4 D Q.5 C Q.6 B Q.7 B

Q.8 B Q.9 A → p, q; B → p, r; C → q; D → q, s Q.10 3 Q.11 6 mL Q.12 (iii) (iv)

Q.16 A → p, q, s; B → p, r, s; C → q, s; D → q, s Q.17 B Q.18 C Q.19 B

Q.20 A Q.21 D Q.22 5 Q.23 D Q.24 B Q.25 5 Q.26 A


2 8. 48 | Co-ordination Compounds

Solutions

JEE Main/Boards Cl Cl
Cl
Cl
Cl

Exercise 1 CO
CO
CO

Sol 1: According to Werner Metal show two types of Cl


linkages /valences namely primary and secondary.
Primary are ionisable and exhibit negative charge.
(ii)
Secondary are non-ionisable. Secondary valency is the NH3
NH3 NH3
coordination no. of central metal atom and is fixed.
Cl Cl

Sol 2: 1: 1 ratio, FeSO4.(NH2)2SO4 is a double salt. So, we CO CO CO

can detect all the ions.


In 2nd case, we get [Cu(NH3)4]2+, so we cannot get Cl
positive test for Cu2+
(iii)
Sol 3: (i) [Cr(C2O4)3] doesn't exhibit geometric isomerism.
3– NH3 NH3 NH3

Cl H3N NH3
(ii) [PtCl2(en)2]2+ has 2 geometrical isomers.
CO CO CO
(iii) [Cr(NH3)2 Cl2(en)] has 2 geometrical isomers. Cl Cl Cl

NH3 Cl Cl

Sol 6: (i) We get a precipitate of CuF2.


Sol 4: (i)
(ii) We get a complex K2[CuCl4].

Leavo Dextro Sol 7: K3[Cu(CN)4] is formed. No precipitate is obtained


because of the lack of Cu2+ ions in the solutions. All the
copper is in complex form.
Cl Cl

Cl Cl
Sol 8:
3d 4s
(ii) 3+
Cr 21e-

3 unpaired e− which do not pair up after hybridisation as


is a weak field ligand.
Cl Cl 3d 4s
2+
Cl Cl Ni 26e-
(iii) (Strong ligand)
H3N NH3
Present even after hybridisation as CN− is a strong field
Sol 5: (i) NH3 NH3 ligand.
Sol 9: Ni2+ is present in both cases but H2O is present
weak ligand
∴ Configuration in 1st Case
Chem i str y | 28.49

3d 4s
2 unpaired e-
3d 4s
3d 4s
Configuration in 2nd Case 2 unpaired
no e--
unpaired e
3d 4s
no unpaired e-

Due to presence of unpaired e– [Ni(H2O)6]2+ is coloured

Sol 10: Both the complexes have Fe2+ as the central metal ion, but H2O is weak ligand, CN– is strong ligand.
3d 4s
3d 4s
[Fe(H2O)6]2+
3d 4s
3d 4s
[Fe(CN)6]4–

Hence, no. of unpaired eΘ are different in both cases which results in different colours in dilute solutions.

Sol 11: (i) K3[Co(C2O4)3]


3d 4s 4p

Co +3 Co.no=6

(ii) [CoF4]2–
3d 4s 4p
Co +2 Co.no=4

(iii) Cis [Cr(en)2Cl2]Cl


3d 4s 4p

Cr +3 Co.no=6

(iv) Mn 2+
3d 4s 4p 4d
Co.no=6

Sol 12: (i)K[Cr(H2O)2(C2O4)2]·3H2O


Potassium diaquadioxalateochromate (III) Trihydrate
3d 4s

Cr +3 Co. No. = 6
2 8. 50 | Co-ordination Compounds

It shows geometric, optical isomerism

MM = 3(5) = 15 BM [
∴ MM = n(n + 2) BM ] where n is no. of unpaired e–
(ii) [Co(NH3)4Cl]Cl2
Tetraammine chloro Cobalt (III) Chloride
3d 4s 4p

Co +3 co. = 5

No stereo isomerism

MM = 4(6) = 24 BM
(iii) CrCl3(py)3
Trichloro Tripyridinium Chromium (III)
3d 4s

Cr +3 Co. No. = 6

Shows geometric isomerism


MM = 3(5) = 15 BM

(iv) Cs(FeCl4) → Caesium Tetrachloro Ferrate (III)


3d 4s 4p

Fe +3 Co. No. = 4

No. isomerism, MM = 5(7) = 35 BM


(v) K4[Mn(CN)6]
Potassium Hexacyano Maganate (II)
3d 4s 4p
Mn +2, Co. No. = 6

No Isomerism, MM = (5) 7 BM = 35 BM

Sol 13: Chelation describes a particular way that ions and molecules bind metal ions. Chelation involves the
formation or presence of two or more separate coordinate bonds between a polydentate ligand and a metal atom.
Chelate effect describes the enhanced affinity of chelating ligands for a metal ion compared to the affinity of
collection of similar non-chelating ligands for same metal.

N CH2 N CH3
Cu is stable than Cu
N CH2 N CH3

Sol 14: (i) [Cr(H2O)6]3+, H2O is weak ligand.


3d 4s

3 unpaired e– i.e. n = 3
Chem i str y | 28.51

(ii) [Fe(H2O)6]2+, H2O is weak ligand Sol 6: (D) Ni → O (zero), dsp2 hybridisation is not
3d 4s
possible.

3 unpaired e– i.e. n = 4 Pd2+ → Square planar

(iii) [Zn(H2O)6]2+, H2O is weak ligand


3d 4s dsp
2

No unpaired e– i.e. n = 0
Sol 7: d4, d5, d6, d7
(ii) Has highest magnetic moment as it has highest no.
of unpaired e– Sol 8: (D) Reasons are vacant d-orbitals and that their

charge to size ratio is large but not that they are metals
Sol 15: Strength of ligands → NO2 > NH3 > H2O
Sol 9: (B) In (A) charge is +4, so there is more donation
∴ Wavelength of [Ni(H2O)6]2+ > [Ni(NH3)6]2+ > [Ni(NO2)6]4– in (A) from Co to O. So B.O. in A is low. So, bond length
is A is higher.
Sol 16: NH+4 cannot form complexes due to lack of lone
pair Sol 10: (C)
a b

a
Sol 17: [Co(NH3)5Cl]2+ A b A
Only 1 Isomer Only 1

A b A b
Exercise 2
b b
Facial Meridional
Single Correct Choice Type
a b
Sol 1: (D) [CoF6]3– doesn't have synergic bonding due to
lack of empty orbitalsA in F–. b A a
Only 1 Isomer Only 1 Isomer
Sol 2: (D) CO, NH3 are
A strong ligands.
b So all are low spin A b
complexes
b b
Facial Meridional
Sol 3: (D) K[Fe(H2O)2(NCS)3NO3]
Potassium di aqua-tri-isothiocynato-nitrato Ferrate (III)
Sol 11: (B) It has 5 CN– ligands (strong) Fe2+, pairing
takes place. So, d2sp3
Sol 4: (B) Fe → 26
3d 4s 4p Sol 12: (A) IUPAC of [Cr(H2O)5ONO]Br2 Penta-aquo-
nitrito-O chromium(III) Bromide

dsp2 (Tetrahedral)
Sol 13: (B) By reduction or dimension, it can attain EAN
CO is a strong ligand. Pairing takes place. of 36. So, oxidation doesn't lead to stability.

Sol 5: (D) NO → NO+, Co2+ → Co3+ (Stable) Sol 14: (D) V2+ because of presence of unpaired e–. Rest
all have no unpaired e–.
Mn+ can form stable complex with strong ligand CO.
Sol 15: (B) Co3+ → 24
So, all are reducing agents
2 8. 52 | Co-ordination Compounds

Previous Years' Questions


2
d sp
3
Sol 1: (C) The number of atoms of the ligand that are
directly bonded to the central metal atom or ion by
So, (b) is correct . In (a) Not exists as NO+ coordinate bond is known as the coordination number
In [Fe(CO)2(NO)2], EAN = 36 (Since not exists as NO+) of the metal atom or ion coordination number of metal
= number of σ bonds formed by metal with ligand.

Sol 16: (B)


Sol 2: (A) CN– ions acts both as reducing agent as well
NH3 NH3 as good complexion agent.

H3 N Cl Cl NH3
Sol 4: (B) + 1 × 4 + x – 1 × 4 = 0
4 + x – 4 = 0 ⇒ x = 0 for Ni.
H3 N Cl H3 N Cl

Cl Sol 5: (C) C.N. of E in complex is 6 and oxidation state is


Cl
Facial Meridional x+0–2–1=0;x=3

Both have plane of symmetries


Sol 6: (B) [Cr(en)2Br2]Br
So, no optical isomer.
Stereo -2 Dibromidobis (ethylenediamine) chromium (III) Bromide.

Sol 17: (B) Mohr's salt has very high mol wt but same Sol 7: (A) Ni2+ in aqueous solution means [Ni(H2O)6]2+.
reducing points. So, its less readily oxidizable than The electronic configuration of
FeSO4 and error in calculations decrease. Ni2+(aq) :
3d
3d
Sol 18: (B) [RhF6] 3–
→ Rh 3+

4s 4p
It's low spin inner orbital complex 4s 4p 4d
4d
3 2
5s 3 sp d hybridization
4d 2
sp d hybridization

Total number of unpaired electron = 2


∴ Spin only magnetic moment of Ni2+ = 2(2 + 2)
Sol 19: (A) Fe3+, weak Tetrahedral = 2 2 = 2.83 B.M.

[Cu(CN)4]3–Cu+ Sol 8: (B) both have 4 unpaired electron.

[AuCl4]–Au3+
Sol 9: (D) cis-form [Co(en)2(NH3)2]3+ has optical isomers.
2
dsp (Square Planar)
2
dsp (Square Planar)
dsp2 (Square Planar)
NH3 NH3 3+ 3+
NH3 NH3
Sol 20: (C) [Co(NH3)6]Cl2
en Co Co en
3 ions i.e. [Co(NH3)6] , 2Cl
2+ –

en en
Mirror
Sol 21: (C) K[Co(CO)4]
CO → Neutral Sol 10: (B) SCN– ion can coordinate through the sulphur
K → +1 ⇒ Co → –1 or nitrogen atom. Such possibilities give rise to linkage
isomerism in coordination compounds.
M ← SCN Thiocyanato or thiocyanato-S
Sol 22: (C) [Fe(C2O4)3]3– is most stable because of chelate
effect M ← NCS Isothiocyanato or thiocyanato-N
Chem i str y | 28.53

Sol 11: (D) 27Co2+ – 1s2 2s2 2p6 3s2 3p6 3d7 4s0 Sol 16: (D)
3d 4s 4p

en

As Cl– is weak field ligand so no pairing up.


Hence it is sp3 hybridized giving tetrahedral geometry.
E ox NO2
Fe2+ – 1s2 2s2 2p6 3s2 3p6 3d6 4s0
3d 4s 4p

en

Due to Cl–, back pairing is not observed so it will be sp3


hybridized giving tetrahedral geometry. Coordination no = 6 and Oxidation no = 3
Ni2+ – 1s2 2s2 2p6 3s2 3p6 3d6 4s0
3d 4s 4p Sol 17: (A) CN- is stronger ligand hence ∆o is highest.

Sol 18: (D) It is octahedral complex of the type [M(AA)2x2]


Because of weak ligand, back pairing is not observed so Where AA is bidentate ligand.
it will be sp3 i.e. tetrahedral geometry. All the complexes
of Pt2+ are square planner including those with weak
field ligand such as halide ions thus (d) is correct. Sol 19: (B) NSC‒ is ambidentate ligand and it can be
linked through N (or) S

Sol 12: (C) In case of d3 configuration, the number


of unpaired electrons remains 3 whether the ligand is Sol 20: (A) CoCl3 .6NH3 → xCl− 
AgNO3
→ x AgCl ↓
strong field or weak field. The hybridization scheme can
be shown as follow
n ( AgCl ) = x n ( CoCl3 .6NH3 )
3d 4s 4p
4.78 2.675
[Cr(NH3)3] = 3+ =x ∴x =3
2 3
143.5 267.5
d sp hybridisation

Hence, the complex is inner orbital complex as it involves ∴ The complex is Co ( NH3 )6  Cl3
(n – 1)d orbitals for hybridization, 3.93 = n(n + 2) ; so
n = 3 (here n is number of unpaired electron(s)). Sol 21: (B) Only option (B) is having non-super
imposable mirror image & hence one optical isomer.

Sol 13: (A) 2Cl– ions are ionizable

∴ [Co(NH3)5Cl]Cl2 [Co(NH3)5Cl]2++2Cl– en
3 ion +2
Zn
2Cl– + 2AgNO3 → 2AgCl + 2NO–3.
NH3

Sol 14: (C) As EDTA is an Hexadentate Ligand, only one NH3


molecule of EDTA will be required to form an octahedral No optical isomer. It is
complex with a Ca2+ ion. Tetrahedral with a plane of symmetry

Sol 15: (B) There is dπ-pπ metal to ligand back bonding


in Fe-C bond of the organometallic compound Fe(CO)5.
So it possesses both σ and π characters.
2 8. 54 | Co-ordination Compounds

en en Red < Yellow < Green < Blue


The complex absorbs lower energy light lower will be its
strength. So order of ligand strength is L1 < L3 < L2 < L4
en +3 +3 en
Co Co
Sol 27: (B) The complex is of the type [Mabcd]
M = metal

en a, b, c, d = Monodentate ligands.
en
H2O a c a c a b
M M M
H2O b d d b d c
+3
Co en 3 geometrical isomers
H2O

H2O Sol 28: (A) Zn2 Fe ( CN)  is white.


Horizontal plane is plane symmetry  6

2+
Sol 29: (A) Each Cr (H2O ) 
2+
and Fe (H2O ) 
en  6  6

+2 Contain 4 unpaired electron.


Zn

Sol 30: (A) With coordination number six, if two


bidentate ligands in cis-position are present, then it is
optically active.
No optical isomer it is
tetrahedral with a plane of symmetry

JEE Advanced/Boards
Sol 22: (B) Cr (NH3 )  Cl3 involves d2 sp3 hybridization
 6
and it is an inner orbital complex. Exercise 1

Sol 23: (B) In NiCl4  , n = 2


2−
Sol 1: [Co(NH)3Cl3] Coordination entity
NH3, Cl → ligand
=
µ n (n + 2 ) BM
Co. no = 6
Polyhedron octahedral, different ligands so
= 2 ( 2 + 2 )= 2.82 BM heteroleptic
[Cr(C2O4)3]3–

Sol 24: (B) Cr ( en) Br2  Br - dibromido bis (ethylene CO24− → ligand
 2 
Co. no = 6
diamine)chromium(III) bromide
Octahedral and homoleptic

Sol 25: (C) Co (NH3 )3 Cl3  show facial as well as


Sol 2: Unidentate → ligand with single e– donor, ex. H2O,
meridional isomerism. But both contain plane of NH3
symmetry. So, the answer is (C).
Bidentate → ligand with two e– donor atoms, ex. C2O24−, en
Ambidentate → ligand with more than 1e– donor atom
Sol 26: (B) The energy of red light is less than that of but both cannot donate pair at the same time.
violet light.
So energy order is
Chem i str y | 28.55

Sol 3: (A) The main basis of the spectrochemical series is If energy released while pairing is higher than D. We get.
the energy difference in the orbitals of the control metal
atom after coming close to the ligands. More is the ∆0, Case - I
stronger is ligand.
(B) else Case - II
NH3 Cl

H3N Cl H3N NH3 Sol 7: [Co(en)2Cl2]Cl


CO CO Dichloro Bisethylene Diamine Cobalt (III) Chloride
H3N Cl H3N Cl Cl
Cl Cl
Facial Meridional
Co

Sol 4:
Py NH3 Py NH3 Cl
Py Pt NH3 Py Pt NH3 Cl Cl

Cl Pt Br Br Pt Cl Cl Cl
Br NH3 Co Co
Cl Br Br Cl
Br Pt NH3

Py Pt Cl

Py Cl dl-pair

No one shows opitcal isomers as all of these are planare dx -y


2 2

and have plane of symmetry.

Sol 5: Stability of a complex in solution refers to the dz


degree of association between the species involved in Sol 8:
the state of equilibrium. d xy
Ex. M + 4L ⇔ ML4
[ML 4 ]
β= dyz, dzx
[M] [L]4
Sol 9: (i) Enzymes
Their stability depends on
•• Chelate effect (ii) Ex. Cisplatin H3N Cl
•• Macrocyclic effect Pt
H3N Cl
•• Geometric factors (like shape)
•• Charge of metal ions (iii) For determining the presence of certain ions using
•• Ionic radius complexing ligands
(iv) Au, Ag Complexes Ex. [Au(CN)2]–
dx -y , dz
2 2 2

Sol 10: If it acts as a chelating agent


Sol 6: 0 ·
: NH2
M
dxy, dyz, dzx : NH2
2 8. 56 | Co-ordination Compounds

There is a formation of 3-membered ring. It's unstable → Linkage Isomerism


Linkage Isomerism
because of high steric hindrance.

M ONO, M NO2
Sol 11: Square planar exhibit geometric isomerism
because of possibility of 2 different locations from a
single location.
→ Coordination Isomerism
AA AA
E.g.
[Co(NH3)6] [Cr(CN)6], [CO(CN)6] [Cr(NH3)6]
MM MM
AA BB Stereo Isomerism
→ Geometrical Isomerism
It's not possible in Tetrahedral. So, it can't show b a b a
geometric isomerism
M M

Sol 12: Let pt 0.5 be x a b b a

x + (–6) = –2 ⇒ x = 4 → Optical Isomerism


Pt → +4 X X

Sol 13: In Hg2Cl2, Hg2Cl2 HgCl2 + Hg X X

HgCl2 + 2NH3 [Hg(NH3)2Cl2]

[Hg(NH2)Cl] + NH4Cl

The liberated mercury renders this precipitate black Sol 17: All the bonds between and ligand are coordinate
covalent bonds.

Sol 14: [Fe(CN)6]3– Fe3+ (i) [Fe(CN)6]4– Fe2+, strong ligand


3d 4s 3d 4s 4p

1 unpaired e

[Fe(CN)6]4– Fe2+
(ii) [FeF6]4– Fe2+, weak ligand
3d 4s
3d 4s 4p 4d
No unpaired e–

Sol 15: n(n + 2) =


5.92 ⇒ n = 5
(iii) [Co(C2O4)3]3– Co3+, strong
i.e. There are 5 unpaired e–
3d 4s 4p
3d 4s

∴ Mn2+

Sol 16: Structural Isomerism (iv) [CoF6]3– Co3+, weak


3d 4s 4p 4d
→ Ionisation Isomerism
[Co(NH3)4Br2]SO4[Co(NH3)SO4]Br2
→ Hydrate Isomerism
(i), (iii) → d2sp3
[Cr(H2O)6]Cl3 [Cr(H2O)5Cl]Cl2 · H2O
(ii), (iv) → sp3d2
Chem i str y | 28.57

Sol 18: The new e– in CO enters into the anti bonding orbitals
of CO and reduces its bond order. The bond order
dx -y , dz
between M and C increase. The extent depends on no.
2 2 2

of lone pairs present on metal for donation. It's called


synergic effect
0
Sol 22: (i) [Co(H2O)CN(en)2]2+
Co +3, Octahedral
dx2-y2, dyz, dzx
(ii) [PtCl4]2–

Sol 19: Spectrochemical series is a series depicting the Pt +2, Square Planar
strength of the ligands during complex formation.
(iii) [Cr(NH3)3Cl3]
Weak field ligand create small ∆o (energy difference b/w
Cr +3, Octahedral
newly formed orbitals) compared to strong field ligands.
So, pairing is not preferred against weak ligands (iv) [CoBr2(en)2]+
Co +3, Octahedral
Sol 20: It's the energy difference between the new
(v) K3[Fe(CN)6]
formed orbitals in the field of a ligand.
If ∆o is high pairing is preferable Fe +3, Octahedral
eg
Sol 23: (i) [Zn(H2O)4]2+
0 3d 4s 4p

t2g
3
sp (Tetrahedral)
for ex. if we take d6 configuration.
(ii) K2[PdCl4]
if ∆o is high is more stable
4d 5s 5p

if ∆o is low is more stable


2
dsp (Square Planar)

Sol 21: In metal carbonyls, CO acts as a ligand and forms


(iii) [Pt(NH3)2Cl2]
5d 6s 6p

CO
2
dsp (Square Planar)
 bond
(iv) K2[Ni(CN)4]
After the formation of σ bonding. There is a possibility 3d 4s 4p
for back bonding from metals to CO.

2
dsp (Square Planar)
CO
(v) [Co(NH3)5ONO]2+
2 8. 58 | Co-ordination Compounds

3d 4s 4p Exercise 2
Single Correct Choice Type
2 3
d sp (Octahedral)
Sol 1: (D) Back bonding in PCl3 > PMe3
(vi) [Co(NH3)6]2(SO4)3
So complex having more PMe3 will save higher back
3d 4s 4p bonding to CO. So, it will have lower C–O bond order.
∴ BO of CO in.

2 3
[M(CO)3(PCl3)3] > [M(CO)3(PCl3)2PMe3] > [M(CO)3PCl3
d sp (Octahedral)
(PMe2)2]
(vii) K3[Cr(C2O4)3]
3d 4s 4p Sol 2: (B) Fe 26
3d 4s 4p

2 3
d sp (Octahedral)
2
dsp (Tetrahedral)
(viii) [Pt(NH3)6]4+
Co is a strong ligand. Pairing takes place.
5d 6s 6p

Sol 3: (D) NO NO+, Co2+ Co3+ (Stable) Mn+


can form stable complex with strong ligand Co.
2 3
d sp (Octahedral)
So, all are reducing agents
(ix) [CoBr4]2–
Sol 4: (A) By reduction or dimension, it can attain EAN
3d 4s 4p
of 36. So, oxidation doesn't lead to stability.

sp
3 Sol 5: (B) Mohr's salt has very high mol wt but same
(Tetrahedral)
reducing points. So, its less readily oxidizable than
FeSO4 and error in calculations decrease.
Sol 24: VBT doesn't account for the difference in
configuration with ligands of different strengths. It also
doesn't account for the colour of complexes. Multiple Correct Choice Type
Where as CFT clearly explains the configurations of Sol 6: (A, C) (A) is true because bridge CO will take e–
metals with different ligands using crystal field model pair from 2 Fe atoms.
so, that we can account for shape, colour and magnetic
properties. (B) is false.

Sol 25: (i) [Co(NH3)4H2OCl]Cl2 N


N N
N
(ii) K2[Zn(OH)4] O
O O
OOO O more repulsion by LP. So angle is less
O
(iii) K3[Al(C2O4)3] (C) is true.
(iv) [CoCl2(NH2 – CH2 – CH2 – NH2)2] + No can also act as acceptor ligand
(v) [Ni(CO)4]
Sol 7: (C, D) (A) Au3+
Diamagnetic

(B) Cu3+
(C) Cu2+ Tetrahedral
Chem i str y | 28.59

a a

A b b A
Paramagnetic, Square Planar

B a a B
(D) Co
b b

b b
Paramagnetic, Square Planar
A a a A

Sol 8: (C, D) Transition elements → last e– enters in B b b B


d-orbital and they are named as such because their a a
properties lie between s and p block.
6 Stereoisomers
Lanthanum is a d-block transition metal
(C) Will have less than (D) as (3), (5) and (4), (6) Coincide
Sol 9: (A, D) (A) (B) Will have more than 6, as we can get 2 for each of
a a (3), (4), (5), (6)

c b b b
Sol 10: (A, B, C) [Fe(CN)6]4– → low spin as CN– is
strong
b c c c
[PtCl4]2– → Pt2+ always forms low spin even with
a a weak ligands

[Co(C2O4)3]3 → low spin as C2O24− is strong ligand


b c
[Ni(NH3)6]2+ →
a a b b
3d 4s 4p 4d

c c a a
3 2
sp d
b c High spin as 6 orbital are needed for hybridisation.
a a Pairing need not occur.
a b b a
Sol 11: (A, B, C) Cu2+ → 1 unpaired e–
Ti3+ → 1
c b b c
Fe3+, strong ligand → 1
c c
[Cr(NH3)6]3+ → 3
(A) Has 6 stereoisomer
(D) [M(AB)A2B2] Sol 12: (A, B, C, D) MA4B2 can't produce due to presence
of plane of symmetry.
b a
MA3B2C will also have plane of symmetry.
A a A b a

a b
B a B b
m has a plane of symmetry
b a
a c

b
2 8. 60 | Co-ordination Compounds

Sol 13: (A, C, D) (A) 22 + 4(2) = 30 Sol 18: (D) Due to synergic bonding M-L bond strength
increases, so complex stability increases More negative
(B) 26 + 2 + 4 (2) = 36 Not exists as NO+
charge of M, increases synergic bonding as more e–
(C) 46 + 2(2) = 50 pairs can be donated.
(D) 78 + 4(2) = 86 Sol 19: (C) C2H2 can act as π-acid ligand All [MA3B2C]
Isomers are optically inactive due to presence of plane
of symmetry. Complex of type [MABCDE2] has 15 active
Sol 14: (B, C, D) NO3− can't show because of no LP on
isomers
N.
O
Paragraph 2:


N - -
O-CN : :S  S  O Sol 20: (C) CN–, because in CO32− , OH– the e– donar.



O O N, Cl have same EN but CN– is a strong ligand


O

Sol 21: (C) Fe 26


Fe2+ 24
Assertion Reasoning Type

Sol 15: (B) Cr+3 → 21e–


eg

t2g as there are 2 d orbitals octahedral

as all ligands are identical, it doesn't show geometrical


isomerism. Sol 22: (B) [V(CO)5]– Metals are mostly unstable under
negative charge
But S-2 doesn't imply S-1
S-1 reason is that t2g orbitals have less energy compared
to eg orbitals. Match the Columns

Sol 23: A → p; B → q, r, t; C → p, q, s; D → q, r, t
a b a b a b
(A) Na[Co(CO)4] monodentate ligand Follows EAN
Sol 16: (C) M M rule M
b a c b d d c (B) c[Pt(triene)Cl2] d no EAN (80) 5 membered ring
M chelating ligand (trien)

c c d (C) [Fe(H2O)5NO]SO4 No EAN (37) all monodentate


NO+ is +ve charged ligand
S-2 is false, as rotation is possible around a single bond (D) [Fe(EDTA)]– hexadentate ligand No EAN 5,
and [MABCD]n± can show geometrical isomerism membered ring (Chelating ligand)

Comprehension Type Sol 24: A → q, s; B → r, s; C → p, q, s


Paragraph 1: (A) [Co(CO)4]– EAN = 36 Synergic bonding is
present Diamagnetic, no isomers
Sol 17: (B) NMe3 only N can donate e– pair. (B) [Zn(sly)2] EAN = 36 dimagnetic, dl pair
SO24− only O can donate e– pair. (C) [Ag(CN)2]– EAN ≠36 (50) There is synergic
Θ
OCN O and N can donate e– pair. bonding It's diamagnetic

So, OCNΘ can show linkage isomerism


Chem i str y | 28.61

Sol 25: A → s; B → p, q, r; C → p; D → q, s (D) [Ma3bcd]


C B B
(A)
A A A A A A
M M M
M M
A B A C A C

D D B
Two optically active isomers C B B
C B B
A A A A A A A A
(B) [M(AB)b
A 2c2] A A A A A
A M B A M B M
A M M A M
A b B A M B A M C A C
A B A C A A C
A C A C
D D B
B Da A D B B
D D
B B A A
A A
B B
A A A B A B
B B
A a A A
M M M M

A b C A C B A C A C
B B

A D D A D D
A A
4 geometric, 2 optically active
A A A B
and
Sol 26: A → q, s; B → r, s; C → p, q, r, t; D → q, r
B A B B
(A) Zn[Fe(CN)5NO] d2sp3, Fe +2, So
B A
diamagnetic, NO NO +

(C) [M(AB)3] (B) [Fe(H2O)5NO]SO4 sp3d2 paramagnetic



A A [ H2O is a weak ligand]NO NO+
B A A B (C) Fe4[Fe(CN)6]3
M M
[Fe(CN)6]4– i.e. F2+ d2sp3
B B B B
There is charge transfer between Fe ions.
A A
B B
Fe3+ Paramagnetic

A A A A (D) K4[Fe(CN)5O2]
M M
Fe3+ d2sp3 and paramagnetic
B B B B
(CN– is strong ligand)
A A

Sol 27: A → r; B → p; C → q; D → s
(A) No. of ions 4
(B) 3
(C) 2
(D) 5
∴C 97 (q)
2 8. 62 | Co-ordination Compounds

B 229 (p) N2+ + 4Cl– → [NiCl4]2–


A 404 (r) Here Ni2+ has d8-configuration with Cl– as weak ligand.
D 523 (s) 3d

3
sp
Previous Years' Questions d8- configuration in weak ligand field gives sp3
hybridisation, hence tetrahedral geometry.
Sol 1: (B) Salt with least no. of unpaired electrons in
Ni2+ with H2O forms [Ni(H2O)6]2+ complex and H2O is a
d-orbital of central metal will show lowest degree of
weak ligand.
paramagnetism.
Mn2+(3d5, 5 unpaired electrons)
Sol 7: (B) (A) Mn+ = 3d54s1 in presence of CO effective
Cu2+(3d9, 1 unpaired electron) configuration = 3d54s0 Three lone pair for back bonding
Fe2+(3d6, 4 unpaired electrons) with vacant orbital of C in CO.
(B) Fe0 = 3d64s2 in presence of CO effective configuration
Ni2+(3d8, 2 unpaired electrons)
= 3d8 four lone pair for back bonding with CO.
Hence, CuSO4 · 5H2O has lowest degree of paramagnetism. (C) Cr0 = 3d54s1 Effective configuration 3d6. Three lone
pair for back bonding with CO.
Sol 2: (D) Cu2+ + CN– CuCN↓ (D) V‒ = 3d44s2 effective configuration = 3d6 three lone
CuCN + 3CN– [Cu(CN)4]3– pair for bonding with CO.
Maximum back bonding is present in Fe(CO)5 there for
CO bond order is lowest here.
Sol 3: (A) In MnO–4, Mn+7 has 3d0 configuration.
Sol 8: (B) Both statements are true. However, axis of
Sol 4: (D) [NiCl4]2– : Ni2+ (3d8) symmetry is not a criteria of optical isomerism. Optical
inactivity of the two geometrical isomers of [M(NH3)4Cl2]
(tetrahedral)
3
is due to presence of lane of symmetry.
sp -hybridisation
Cl NH3
H3N NH3 H3N Cl
8
3d 4s
M M
Under influence of weak
Lignad field
H3N NH3 H3N Cl
In all other complexes, hybridization at central metal is Cl NH3
trans cis
dsp2 and complexes have square planar geometries. (has several planes of symmetry) (has several planes of symmetry)

Sol 5: (C) [Ni(NH3)4]2+ = tetraamminenickel (II)


[NiCl4]2– = tetrachloronickelate (II) Sol 9:
Cationic part is named first, hence : 2+ 2+
OH2 NH3
tetraamminenickel (II)-tetrachloronickelate(II) NH3 OH2
H3N H2O
(A) Co Co

Sol 6: (B) Ni2+ + 4CN– → [Ni(CN)4]2– H3N NH3 H3N NH3


OH2 OH2
Here Ni2+ has d8-configuration which CN– as strong
(trans) (cis)
ligand 2+ 7
Co =3d (Paramagnetic)
8
3d 4s 4p
[Pt(NH3)2Cl2] is square planar.

H3N Cl H3N Cl
2 2+ 2+
dsp (B) Pt Pt

d -configuration in strong ligand field gives dsp


8 2 H3N Cl Cl NH3

hybridisation, hence square planar geometry. 2+ 8


(cis)
0
(trans)
Pt =5d 4s (Diamagnetic)

+ (D) +
(C)
OH2 OH2
OH OH
2+ 2+
(B) Pt Pt

H3N Cl Cl NH3

2+ 8
(cis)
0
(trans)
Chem i str y | 28.63
Pt =5d 4s (Diamagnetic)

(C)
+ (D) + Sol 13:
OH2 OH2
OH2 OH2 NH3
H2O H2O
H3N NH3
Co Co
H2O OH2 H2O OH2
Cl OH2 Co
2+ 7 2+ 8
Co =3d (Paramagnetic) Ni =3d (weak field ligand, paramagnetic)
H 3N NH3 OC
NH3
d2sp3-octahedral dsp2-square planar

Sol 10:
NH3 CO
Cl PPh
H3N3 Cl NH3 CO

Rh Rh Ni
Co CO
H3N CO H3N PPh3
H 3N OC CO
NH3
NHPPh sp -tetrahedral
3
Cl 3
3

Rh
Sol 14: The spin-only magnetic moment (µ) of the
OC H 3N
3 isomers complex is 1.73 BM. It indicates that nucleus of complex,
chromium ion has one unpaired electron. So, the ligand
Sol 11: m mol of complex = 30 × 0.01 = 0.3 NO is unit positively charged.
Also, 1 mole of complex [Cr(H2O)5Cl]Cl2 gives only tow K2[Cr(NO) (CN)4 (NH3)]
moles of chloride ion when dissolved in solution Potassium ammine tetracyanonitrosonium-chromate (I)
[Cr(H2O)5Cl]Cl2 [Cr(H2O)5Cl] + 2Cl 2+ –

CrCr+1 :
+1

⇒ m mol of Cl ion produced from its 0.3 m mol = 0.6



3d
5
4s
0

Hence, 0.6 m mol of Ag+ would be required for Cr(I) “under influence of strong ligand field”.
precipitation.
⇒ 0.60 m mol of Ag+ = 0.1M × V(in mL) ⇒ V = 6 mL.
2 3
d sp
octahedral
Sol 12: (i) [Ti (NO3)4] : Ti4+ (3d0) No d-electron, no d-d
transition possible, colourless.
NO
(ii) [Cu(NCCH3)]BF4 : Cu+ (3d10) All d-orbitals are NC CN
completely filled, no d-d transition possible, colourless.
(iii) [Cr(NH3)6]Cl3 : Cr3+ (3d3) Complex has allowed d-d M
transitions from t2g to eg level, hence, coloured.
NC NH3
(iv) K3[VF6] : V3+ (3d2) Complex has allowed d-d transitions CN
from t2g to eg level, hence, coloured.
Sol 15: Oxidation state of Ni is +2 and hybridization is
dsp2. µ = 0
H H
O O
(nounpaired electron). H3C N N CH3
C C
Ni
C C
N N CH3
H3C
O O
H H
2 8. 64 | Co-ordination Compounds

Sol 16: (A) Fe (H2O )5 NO  SO 4


(s) d − d σ anticoding
Here Fe has +1 oxidation state.
Fe+ = 3d64s1 in presence of NO+ 4s1 electron are paired
in 3d sub shell.
Sol 21: (D) [Fe(SCN)6]3– and [Fe(CN)6]3–. In both the cases
So electronic configuration of Fe+ is
the electronic configuration of Fe3+ will be 1s2, 2s2, 2p6,
3p6, 3d5. Since SCN is a weak field ligand and CN is a
strong field ligand, the pairing will occur in case of
3d

5
(high spin)
Case-1 3d
Sol 17: (D) Co (H2O ) 4 (NH3 )2 Cl3 
(no pairing)

Diamminetetraaquacobalt (III) chloride (low spin)


Case-2 (pairing)

Sol 18: (B) P = Fe (no. of unpaired e = 5 )


+3

Q = V+2 (no. of unpaired e = 3 ) Case-1 µ= n ( n + 2 )= 5 (5 + 2 ) = 35= 5.91 BM


R = Fe+2 (no. of unpaired e = 4 ) 3
Case-2 µ = n (n + 2 ) = 1 (1 + 2 ) = =1.73 BM
As all ligands are weak field, hence the no. of unpaired
electrons remains same in the complex ion.
Sol 22: (5) [Co(en2Cl2)]+ → will show cis - trans isomerism
=µ n (n + 2 )B.M
[CrCl(C2O4)]3‒ → will show cis - trans isomerism
Hence (B) is correct.
[Fe(H2O)4(OH)2]+ → will show cis trans isomerism

+
[Fe(CN)4(NH)3]‒ → will show cis trans isomerism
Sol 19: (B, D) Co (NH3 ) Cl2  and Pt (NH3 )2 (H2O ) Cl
+
 4  [Co(en)2(NH3)Cl]2+ → will show cis trans isomerism
(a square planar complex) will show geometrical [Co(NH3)4(H3O)Cl]2+ → Will not show cis – trans isomerism
isomerism.
(Although it will show geometrical isomerism)
Pt (NH ) (NO )  Cl and Pt (NH3 ) Cl Br will show
 3 3 3   3 
ionization isomerism. Sol 23: (D)
PEt3 O
Sol 20: (C) Et3P CH3
C
Fe

(p) d − dσ  bonding OC Br
CO

Sol 24: (B) [Ni(CO)4] ‒ sp3 ‒ Diamagnetic


(q) p − dπ bonding [NiCl4]2‒ ‒ sp3 ‒ Paramagnetic
[Co(NH3)4 Cl2]Cl2 ‒ d2sp3 ‒ Diamagnetic
Na3 [CoF6] ‒ sp3d2 Paramagnetic
(r) p − dπ anticoding Na i.e O22− −‒ Diamagnetic
Na22OO22 i.e.
i.e O2− −‒ Paramagnetic
CsO2 i.e.
Chem i str y | 28.65

Sol 25: (5)


Cl Cl

NH2 NH2 NH2 O

CH2 +3 CH2 CH2 +3 CH2


Co Co

CH2 CH2 CH2 CH2


O O O NH2
CH2 CH2
Cl Cl
NH2 CH2 O CH2

NH2 O NH2 NH2

CH2 +3 CH2 +3
Co Co
CH2 CH2

O Cl O Cl
Cl Cl
CH2
O CH2

CH2 +3
Co
CH2

NH2 Cl
Cl

Sol 26: (A) [Ni(NH3)6]2+ = Octahedral


[Pt(NH3)4]+2 = Square planar
[Zn(NH3)4]+2 = Tetrahedral

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