AL-MADINAH PUBLIC SCHOOL GRADE-XII CHEMISTRY

CHAPTER-9
COORDINATION CHEMISTRY
Previous year questions
1. Distinguish between double salt and coordination complex.
Sl.No Double salt Coordination complex
1. When dissolved in water, double salts Coordination compounds are water soluble
are completely dissociated into simple and separated into complex ion and counter
ions. ion.
2. Double salts give test for all their Coordination complexes do not give test for
constituent ions. all their constituent ions.
3. Double salts contain ionic bonds Coordinate compounds contain coordinate
between cations and anions. covalent bonds between metal ion and
ligands.
4. Eg. Mohr’s salt FeSO4(NH4)2SO4⋅6H2O Eg. Potassium ferrocyanide K4 [Fe(CN)6 ]

2. Why does NH3 take part in complex formation but not NH4+?
NH4+ ion does not take part in complex formation because
 unlike NH3, the N-atom of NH4+ does not have any lone pair of electrons.
 The positive charge on NH4+ gets repelled by the positively charged metal ion.
3. The Coordination number of Ag in [Ag(NH3)2]Cl is:
Ans: 2
4. Define ambidentate ligand with example.
A molecule or an ion which contains two donor atoms but only one of them forms a coordinate
bond at a time with the central metal ion is called ambidentate ligand, e.g., CN– or NC– and NO2- or
ONO-.
5. What is meant by chelate effect? Give an example. (OR)
What is a chelate complex? Give an example.
When a bidentate or a polydentate ligand contains donor atoms coordinate with the central
metal ion, a five or a six-membered ring is formed, this effect is called chelate effect.
Example, [PtCl2(en)].

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6. What is the difference between an ambidentate ligand and a chelating ligand?

Sl.No. Ambidentate ligand Chelating ligand
1. A molecule or an ion which contains When a bidentate or a polydentate ligand
two donor atoms but only one of them contains donor atoms coordinate with the
forms a coordinate bond at a time with central metal ion, a five or a six-membered
the central metal ion is called ring is formed, it is called a chelating
ambidentate ligand. ligand.
2. Eg: CN– or NC– and NO2- or ONO-. Eg: ethane-1,2-diamine (en), EDTA4-

7. What are homoleptic and heteroleptic complexes? Give examples.

Homoleptic Complex: The complex in which metal atom is bound to only one kind of donor groups
(ligands), e.g., [Cu(CN)4]3–.
Heteroleptic Complex: The complex in which metal atom is bound to more than one kind of donor
groups (ligands), e.g., [Co(NH3)4Cl2]+.
8. Write IUPAC names of the following coordination compounds:
(i) [CoCl2(en)2]+ - Dichloridobis(ethane-1,2-diamine)cobalt(III) ion
(ii) K3 [Fe(CN)6] - Potassium hexacyanidoferrate(III)
(iii) [CoF6]3– - Hexafluoridocobaltate(III) ion
(iv) [Ni(CO)4] - Tetracarbonylnickel (0)
3+
(v) [Co(NH3)6] - Hexaamminecobalt(III) ion
(vi) [NiCl4]2– - Tetrachloridonickelate(II) ion
(vii) [Fe(CN)6]3– - Hexacyanidoferrate(III) ion
(viii) K3[Cr(C2O4)3] - Potassium tri(oxalato)chromate(III)
9. Write the formulas for the following coordination compounds:
(i) Iron(III) hexacyanidoferrate(II) - Fe4 [Fe(CN)6]3
(ii) Dichloridobis(ethane-1,2-diamine)cobalt(III) - [CoCl2(en)2]+
(iii) Potassium tetrahydroxozincate(II) – K2 [Zn(OH)4]
(iv) Hexaammineplatinum(IV) Chloride - [Pt(NH3)6] Cl4
(v) Potassium trioxalatoaluminate(III) - K3[Al(C2O4)3]
(vi) Tetraammineaquachloridocobalt(III) Chloride - [Co(NH3)4(H2O)Cl]Cl2
(vii) Pentaamminecarbonatocobalt(III) chloride – [Co(NH3)5(CO3)] Cl
(viii) Potassium tetracyanidonickelate(II) – K2 [Ni(CN)4 ]
(ix) Tetraammineaquachloridocobalt (III) nitrate - [Co(NH3)4(H2O)Cl](NO3)2
(x) Potassium trioxalatochromate(III) - K3 [Cr(C2O4)3]

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(xi) Hexaamminecobalt(III) sulphate - [Co(NH3)6]2 (SO4)3

(xii) Sodium tetrachloridonickelate(II) - Na2 [NiCl4]
(xiii) Pentaamminenitrito-O-cobalt(III) - [Co(NH3)5(ONO)]2+
(xiv) Dichloridobis(ethane-1,2-diamine)platinum(IV) nitrate - [PtCl2 (en)2 ] (NO3)2
10. The compound PtCl2 ⋅ 2NH3 does not react with AgNO3 , what will be its formula?
Ans: [Pt(NH3)2Cl2]
11. When a coordination compound NiCl2. 6H2O is mixed with AgNO3, 2 moles of AgCl are
precipitated per mole of the compound. Write:
(i) Structural formula of the complex - [Ni(H2O)6] Cl2
(ii) Secondary valency of Ni in the complex - Six
(iii) IUPAC name of the complex - Hexaaquanickel (II) chloride.
12. When a coordination compound CrCl3.6H2O is mixed with AgNO3, 2 moles of AgCl are
precipitated per mole of the compound. Write
(i) structural formula of the complex - [Cr(H2O)5Cl]Cl2.H2O
(ii) IUPAC name of the complex - Pentaaquachloridochromium (III) chloride monohydrate
13. What is the secondary valency of [Co(en)3]3+ ?
Ans: Six
14. What is the secondary valency of cobalt in [Co(en)2Cl2]+?
Ans: Six
15. What is the coordination number of the metal ion in an octahedral complex?
The coordination number of the metal ion in an octahedral complex = 6.
16. Write the hybridization and magnetic character of [FeF6]3–.
Electronic configuration of Fe (Z=26) = [Ar] 3d6 4s2
Iron in [FeF6]3– is +3 oxidation state.
Electronic configuration of Fe3+ = [Ar] 3d5 4s0

F- is a weak field ligand, so it does not pairing of electrons.

Hybridization: sp3 d2
Geometry: Octahedral, outer orbital complex, high spin complex.
Magnetic property: Since five electrons are unpaired, it is paramagnetic.

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The spin-only magnetic moment (μ) = 𝑛 (𝑛 + 2) = 5 (5 + 2) = 35 = 5.83 BM.

17. Write the hybridization and magnetic characters of the following complexes:
(i) [Fe(CN)6]4– (ii) [CoF6]3–
(i) [Fe(CN)6]4– :
Electronic configuration of Fe (Z=26) = [Ar] 3d6 4s2
Iron in [Fe(CN)6]4– is +2 oxidation state.
Electronic configuration of Fe2+ = [Ar] 3d6 4s0

CN- is a strong field ligand, so it causes pairing of electrons.

Hybridization: d2 sp3
Geometry: Octahedral, inner orbital complex, low spin complex.
Magnetic property: Since the absence of unpaired electrons, it is diamagnetic.
(ii) [CoF6]3– :
Electronic configuration of Co (Z=27) = [Ar] 3d7 4s2
Cobalt in [CoF6]3– is +3 oxidation state.
Electronic configuration of Co3+ = [Ar] 3d6 4s0

F- is a weak field ligand, so it does not pairing of electrons.

Hybridization: sp3 d2
Geometry: Octahedral, outer orbital complex, high spin complex.
Magnetic property: Since four electrons are unpaired, it is paramagnetic.
The spin-only magnetic moment (μ) = 𝑛 (𝑛 + 2) = 4 (4 + 2) = 24 = 4.89 BM.
18. [NiCl4]2– is paramagnetic while [Ni(CO)4] is diamagnetic though both are tetrahedral. Why?
[NiCl4]2–:
Electronic configuration of Ni (Z=28) = [Ar] 3d8 4s2
Nickel in [NiCl4]2– is in the +2 oxidation state.
Electronic configuration of Ni2+ = [Ar] 3d8 4s0

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Cl – is a weak field ligand. It is, therefore, unable to pair up the unpaired electrons.
Hybridization: sp3
Geometry: Tetrahedral
Magnetic property: Since two electrons are unpaired, it is paramagnetic.
The spin-only magnetic moment (μ)

[Ni(CO)4]:
Electronic configuration of Ni (Z=28) = [Ar] 3d8 4s2
Nickel in [Ni(CO)4] is in zero oxidation state.
Electronic configuration of Ni (0) = [Ar] 3d8 4s2

CO is a strong field ligand, so it causes pairing of electrons.

Hybridization: sp3
Geometry: Tetrahedral
Magnetic property: Since absence of unpaired electrons, it is diamagnetic.
19. Write the hybridization and magnetic character of [Fe(CO)5]
Electronic configuration of Fe (Z=26) = [Ar] 3d6 4s2
Iron in [Fe(CO)5] is in zero oxidation state.
Electronic configuration of Fe (0) = [Ar] 3d6 4s2

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CO is a strong field ligand, so it causes pairing of electrons.

Hybridization: dsp3
Geometry: trigonal bipyrimidal
Magnetic property: Since the absence of unpaired electrons, it is diamagnetic.
20. A solution of [Ni(H2O)6]2+ is green but a solution of [Ni(CN)4]2– is colourless. Explain.
[Ni(H2O)6]2+ :
Electronic configuration of Ni (Z=28) = [Ar] 3d8 4s2
Nickel in [Ni(H2O)6]2+ is in the +2 oxidation state.
Electronic configuration of Ni2+ = [Ar] 3d8 4s0

Hybridization: sp3 d2
Geometry: Octahedral, outer orbital complex, high spin
complex.

[Ni(H2O)6]2+ has two unpaired electrons which do not pair up in the presence of the weak H2O
ligand. So, it is coloured. The d–d transition absorbs red light and the complementary light emitted
is green.
[Ni(CN)4]2–:
Electronic configuration of Ni (Z=28) = [Ar] 3d8 4s2
Nickel in [Ni(CN)4]2– is in the +2 oxidation state.
Electronic configuration of Ni2+ = [Ar] 3d8 4s0

CN- is a strong field ligand, so it causes pairing of electrons.

Hybridization: dsp2
Geometry: Square planar

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In case of [Ni(CN)4]2–, in presence of the strong CN– ligand, the two unpaired electrons in the 3d
orbitals pair up. Hence, there is no unpaired electron present. Hence, it is colourless.
21. Using valence bond theory, predict the hybridization and magnetic character of
[Co(C2O4)3]3–
Electronic configuration of Co (Z=27) = [Ar] 3d7 4s2
Cobalt in [Co(C2O4)3]3– is +3 oxidation state.
Electronic configuration of Co3+ = [Ar] 3d6 4s0

Oxalate is a bi-dentate ligand, so pairing of electrons takes place.

Hybridization: d2 sp3
Geometry: Octahedral, inner orbital complex, low spin complex.
Magnetic property: Since the absence of unpaired electrons, it is diamagnetic.
22. The molecular shape of Ni(CO)4 is not the same as that of [Ni(CN)4]2- why?
Ni(CO)4 :
Electronic configuration of Ni (Z=28) = [Ar] 3d8 4s2
Ni is in zero oxidation state
Ni(0) = [Ar] 3d8 4s2
CO is a strong field ligand causes pairing of electrons.

sp3 hybridization
[Ni(CO)4] has sp3 hybridization and has tetrahedral shape.

It has square planar geometry.

Ni in Ni(CO)4 is zero oxidation state and [Ni(CN)4]2- is +2 oxidation state, so their geometry
are not the same.
23. Why are low spin tetrahedral complexes not formed?
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Low spin tetrahedral complexes are not formed because for tetrahedral complexes, the crystal
field stabilization energy is less than pairing energy.
24. On the basis of crystal field theory, write the electronic configuration of d4 ion if Δ0 < P.
If Δ0 < P (pairing energy), the 4th electron enters one of the eg orbitals, and the configuration
will be t32g e1g, in case of weak field ligands and high spin complex will be formed.
25. On the basis of crystal field theory, write the electronic configuration of d4 ion if Δ0 > P.
If Δ0 > P, the 4th electron pairs up in one of the t2g orbitals giving the configuration t42g e0g, in
case of strong field ligands and low spin complex will be formed.
26. Using crystal field theory, draw energy level diagram, write electronic configuration of the
central metal atom/ion and determine the magnetic moment value in the [Fe(H2O)6]2+.

27. Write the electronic configuration of Fe(III) on the basis of crystal field theory when it forms
an octahedral complex in the presence of (i) strong field ligand, and (ii) weak field ligand.
Electronic configuration of Fe (Z=26) = [Ar] 3d6 4s2
Electronic configuration of Fe 3+ = [Ar] 3d5

In case of strong field ligand- Fe(III) = t2g 5 eg0

In case of weak field ligand- Fe(III) = t2g 3 eg2
28. Give the IUPAC name, oxidation state, coordination number, stereochemistry and electronic
configuration of central metal atom in terms of t2g and eg of K4[Mn(CN)6].
K4[Mn(CN)6] :
IUPAC name: Potassium hexacyanomanganate(II)
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Oxidation state of Mn = +2, coordination number = 6

Stereochemistry = octahedral
Electronic configuration of Mn2+: [Ar] 3d5 4s0 = (t2g)5 (eg)0
The spin-only magnetic moment (μ) = 𝑛 (𝑛 + 2) = 1 (1 + 2) = 3= 1.73 BM.
29. What type of isomerism is shown by the complex [Cr(H2O)5Br]SO4 ?
(i) Ionisation isomerism: [Cr(H2O)5Br]SO4 and [Cr(H2O)5 (SO4)]Br
(ii) Hydrate or solvate isomerism: [Cr(H2O)5Br]SO4 and [Cr(H2O)4 (Br)( SO4)] H2O
30. Isomerism exhibited by the compounds [Co(SO4)(NH3)5]Br and [Co(Br)(NH3)5] SO4 is?
Ans: Ionisation isomerism
31. What type of isomerism is shown by the complex [Co(NH3)5 NO2] Cl2?
It exhibits both ionization and linkage isomerism.
[Co(NH3)5 (NO2)] Cl2 and [Co(NH3)5 (ONO)] Cl2 (linkage isomerism)
[Co(NH3)5 (NO2)] Cl2 and [Co(NH3)5 (Cl)] (Cl) (NO2) (ionization isomerism)
32. What type of isomerism is shown by the complex [Co(en)2Cl2]2+ ? Name the structure of an
isomer of this complex which is optically active.
[Co(en)2Cl2]2+ shows geometrical (cis-trans) isomerism.

Cis- isomer of [Co(en)2Cl2]2+ shows optical activity. Its IUPAC name is cis-Dichloridobis(ethane-
1,2-diamine)cobalt(IV) ion
33. Write IUPAC name of the complex [Pt(en2)Cl2]. Draw structures of geometrical isomers for
this complex.
IUPAC name of this complex is Dichloridobis(ethane-1,2-diammine)platinum(II).

cis trans
34. Out of Cis–[Pt(en)2Cl2]2+ and Trans–[Pt(en2)Cl2]2+, which one is optically active and why?

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Only cis-form will have non-superimposable mirror images. Trans isomer is optically inactive
as it has mirror plane and hence symmetry.

35. Give evidence that [Co(NH3)5Cl]SO4 and [Co(NH3)5SO4]Cl are ionization isomers. (OR)
How can you show that complexes [Co(NH3)5Cl]SO4 and [Co(NH3)5SO4]Cl are ionization
isomers ?
 Add BaCl2 solution, [Co(NH3)5Cl]SO4 will give white precipitate due to the formation of
BaSO4, but [Co(NH3)5SO4]Cl will not react.
 Add AgNO3 solution [Co(NH3)5SO4]Cl will give white precipitate due to the formation of
AgCl, but [Co(NH3)5Cl]SO4 will not react.
 These isomers produce different ions in aqueous solution but have same chemical formula,
therefore they are ionization isomers.
36. Write the IUPAC name of the isomer of the following complex: [Pt(NH3)2Cl2]
cis-diamminedichloridoplatinum (II) and trans-diamminedichloridoplatinum (II)
37. How is stability of coordination compounds determined in aqueous solution?
 Higher the value of stability constant, greater will be the stability.
 Smaller the cation, higher charge on cation, more stable will be the complex.
 Chelating agents form more stable complexes.
 Stronger the ligand, more stable will be the complex.
38. Amongst the following, which complex is the most stable and why?
(i) [Fe(H2O)6]3+ (ii) [Fe(NH3)6]3+ (iii) [Fe(C2O4)3]3– (iv) [FeCl6]3–
[Fe(C2O4)3]3–, because oxalate is a bi-dentate ligand. It will form a stable chelating ring with
central metal ion.
39. Which of the following is more stable complex and why? [Co(NH3)6]3+ and [Co(en)3]3+
[Co(en)3]3+ is more stable complex because ethane-1,2-diamine is a bi-dentate ligand. It will
form a stable chelating ring with central metal ion.
40. Discuss the nature of bonding in metal carbonyls.
The metal–carbon bond in metal carbonyls have both σ and π character. The metal–carbon σ -
bond is formed by the donation of lone pair of electrons from the carbonyl carbon into a vacant
orbital of the metal. The metal–carbon π -bond is formed by the donation of a pair of electrons
from a filled d-orbital of metal into the vacant anti-bonding π -molecular orbital (π *) of carbon

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monoxide. The metal to ligand bonding creates a synergic effect which strengthens the bond
between CO and the metal.

41. Write the role of coordination compounds with examples in each of the following:
(i) Biological system (ii) Extraction/Metallurgy of metals
(i) In Biological System:
 Haemoglobin, the red pigment of blood which acts as oxygen carrier is a complex of Fe2+
with porphyrin.
 The pigment responsible for photosynthesis, chlorophyll, is a complex of Mg2+ with
porphyrin.
 Vitamin B12 (Cyanocobalamine), the antipernicious anaemia factor, is a complex of cobalt.
(ii) Extraction/metallurgy of metals:
 In Mond’s process, impure nickel is converted to [Ni(CO)4], which is decomposed to yield
pure nickel.
 Silver and gold are extracted from their ores as cyanide complex.
NCERT in-text questions
42. Write the formulas for the following coordination compounds:
(i) Tetraamminediaquacobalt(III) chloride - [Co(NH3)4 (H2O)2]Cl3
(ii) Tris(ethane-1,2-diamine)chromium(III) chloride - [Cr(en)3 ]Cl3
(iii) Amminebromidochloridonitrito-N-platinate(II) - [Pt(NH3) Br Cl (NO2)]-
43. Write IUPAC names of the following coordination compounds:
(i) [Co(NH3)6]Cl3 - Hexaamminecobalt(III) chloride
(ii) [Co(NH3)5Cl]Cl2 - Pentaamminechloridocobalt(III) chloride
(iii) K3 [Fe(C2O4)3] - Potassium trioxalatoferrate(III)
(iv) K2 [PdCl4] - Potassium tetrachloridopalladate(II)
(v) [Pt(NH3)2Cl(NH2CH3)]Cl - Diamminechlorido(methylamine)platinum (II) chloride
44. Indicate the types of isomerism exhibited by the following complexes and draw the structures
for these isomers:
(i) K[Cr(H2O)2 (C2O4)2]

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Both geometrical (cis–trans) and optical isomers for cis can exist.

(ii) [Co(en)3]Cl3

(iii) [Co(NH3)5 (NO2)] (NO3)2

It exhibits both ionization and linkage isomerism.
[Co(NH3)5 (NO2)] (NO3)2 and [Co(NH3)5 (ONO)] (NO3)2 (linkage isomerism)
[Co(NH3)5 (NO2)] (NO3)2 and [Co(NH3)5 (NO3)] (NO3) (NO2) (ionization isomerism)
(iv) [Pt(NH3)(H2O)Cl2]

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45. Explain on the basis of valence bond theory that [Ni(CN)4]2– ion with square planar structure
is diamagnetic and the [NiCl4]2– ion with tetrahedral geometry is paramagnetic.
[Ni(CN)4]2–:
Electronic configuration of Ni (Z=28) = [Ar] 3d8 4s2
Nickel in [Ni(CN)4]2– is in the +2 oxidation state.
Electronic configuration of Ni2+ = [Ar] 3d8 4s0

CN- is a strong field ligand, so it causes pairing of electrons.

Hybridization: dsp2
Geometry: Square planar
Magnetic property: Since no unpaired electron is present, [Ni(CN)4]2– is diamagnetic.
[NiCl4]2–:
Electronic configuration of Ni (Z=28) = [Ar] 3d8 4s2
Nickel in [NiCl4]2– is in the +2 oxidation state.
Electronic configuration of Ni2+ = [Ar] 3d8 4s0

Cl – is a weak field ligand. It is, therefore, unable to pair up the unpaired electrons.
Hybridization: sp3
Geometry: Tetrahedral
Magnetic property: Since two electrons are unpaired, it is paramagnetic.
The spin-only magnetic moment (μ)

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46. [Fe(H2O)6]3+ is strongly paramagnetic whereas [Fe(CN)6]3– is weakly paramagnetic. Explain.

[Fe(H2O)6]3+ :
Electronic configuration of Fe (Z=26) = [Ar] 3d6 4s2
Iron in [Fe(H2O)6]3+ is +3 oxidation state.
Electronic configuration of Fe3+ = [Ar] 3d5 4s0

H2O is a weak field ligand. It is, therefore, unable to pair up the unpaired electrons.
Hybridization: sp3 d2
Geometry: Octahedral, outer orbital complex, high spin complex.
Magnetic property: Since five electrons are unpaired, it is strongly paramagnetic.
The spin-only magnetic moment (μ) = 𝑛 (𝑛 + 2) = 5 (5 + 2) = 35 = 5.92 BM.
[Fe(CN)6]3– :
Electronic configuration of Fe (Z=26) = [Ar] 3d6 4s2
Iron in [Fe(CN)6]3– is +3 oxidation state.
Electronic configuration of Fe3+ = [Ar] 3d5 4s0

CN- is a strong field ligand, so it causes pairing of electrons.

Hybridization: d2 sp3
Geometry: Octahedral, inner orbital complex, low spin complex.
Magnetic property: Since only one electrons is unpaired, it is weakly paramagnetic.

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The spin-only magnetic moment (μ) = 𝑛 (𝑛 + 2) = 1 (1 + 2) = 3 = 1.73 BM.

47. Explain [Co(NH3)6]3+ is an inner orbital complex whereas [Ni(NH3)6]2+ is an outer orbital
complex.
[Co(NH3)6]3+:
Electronic configuration of Co (Z=27) = [Ar] 3d7 4s2
Cobalt in [Co(NH3)6]3+ is +3 oxidation state.
Electronic configuration of Co3+ = [Ar] 3d6 4s0

NH3 is a strong field ligand, so it causes pairing of electrons.

Hybridization: d2 sp3
Geometry: Octahedral, inner orbital complex, low spin complex.
Magnetic property: Since absence of unpaired electrons, it is diamagnetic.
[Ni(NH3)6]2+ :
Electronic configuration of Ni (Z=28) = [Ar] 3d8 4s2
Nickel in [Ni(NH3)6] 2+ is in +2 oxidation state.
Electronic configuration of Ni2+ = [Ar] 3d8 4s0

Here pairing of unpaired electrons does not take place.

Hybridization: sp3 d2
Geometry: Octahedral, outer orbital complex, high spin complex.
Magnetic property: Since two electrons is unpaired, it is paramagnetic.
The spin-only magnetic moment (μ) = 𝑛 (𝑛 + 2) = 2 (2 + 2) = 8 = 2.82 BM.
48. Predict the number of unpaired electrons in the square planar [Pt(CN)4]2– ion.
Electronic configuration of Pt (Z=78) = [Xe] 5d9 6s1

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Platinum in [Pt(CN)4]2– ion is in +2 oxidation state.

Electronic configuration of Pt2+ = [Xe] 5d8 6s0

Since CN- is a strong field ligand, it pair up the unpaired electrons. It has dsp2 hybridization, square
planar geometry and no unpaired electrons.
49. The hexaaqua manganese(II) ion contains five unpaired electrons while the hexacyano ion
contains only one unpaired electron. Explain using crystal field theory.
[Mn(H2O)6]2+ [Mn(CN)6]4-
Mn is in the +2 oxidation state. Mn is in the +2 oxidation state.
The electronic configuration is 3d5. The electronic configuration is 3d5.

The crystal field is octahedral. Water is a The crystal field is octahedral. Cyanide is a strong
weak field ligand. Therefore, the arrangement field ligand. Therefore, the arrangement of the
of the electrons in [Mn(H2O)6]2+ is t2g3eg2. electrons in [Mn(CN)6]4- is t2g5eg0.
Hence, hexaaquo manganese (II) ion has five While hexacyano ion has only one unpaired
unpaired electrons electron.

NCERT Exercises:
50. Explain the bonding in coordination compounds in terms of Werner’s postulates.
The main postulates of this theory are:
(i) In coordination compounds, metals show two types of valencies: primary and secondary.
(ii) The primary valencies are normally ionisable and are satisfied by negative ions.
(iii) The secondary valencies are non ionisable and are satisfied by neutral molecules or negative
ions. The secondary valency is equal to the coordination number and is fixed for a metal.
(iv) The ions or groups bound by secondary linkage to the metal have characteristic spatial
arrangements.

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51. FeSO4 solution mixed with (NH4)2SO4 solution in 1:1 molar ratio gives the test of Fe2+ ion but
CuSO4 solution mixed with aqueous ammonia in 1:4 molar ratio does not give the test of Cu2+
ion. Explain why.
FeSO4 solution mixed with (NH4)2SO4 solution in 1:1 molar ratio forms double salt FeSO4 .
(NH4)2 SO4.6H2O which ionises in the solution to give Fe2+ ions. Hence, it gives the test of Fe2+
ions.
CuSO4 solution mixed with aqueous ammonia in 1:4 molar ratio forms a complex, with the
formula [Cu(NH3)4]SO4. The complex ion, [Cu(NH3)4]2+ does not ionise to give Cu2+ ions. Hence,
it does not give the test of Cu2+ ion.
52. Explain with two examples for each of the following: Coordination entity, ligand,
coordination number, coordination polyhedron.
Coordination Entity: A coordination entity constitutes a central metal atom or ion bonded to a fixed
number of molecules or ions (ligands), e.g., [Co(NH3) Cl3 ], [Fe(CN6)]4-.
Ligands: Ligands are the atoms, molecules or ions which donate a pair of electrons to central metal
atom or ion and form a coordinate bond with it. Example: NH3, Cl-, CN-.
Coordination Number (CN): The total number of ligand donor atoms to which the metal ion is
directly bonded is called coordination number. For example, in the complex ions, [Co(NH3)6]3+ and
[Fe(C2O4)3]3– the coordination numbers of both Co and Fe is 6.
Coordination Polyhedron: The spatial arrangement of the ligand atoms which are directly attached
to the central atom/ion is known as the coordination polyhedron. Tetrahedral, square planar,
octahedral, square pyramidal and trigonal bipyramidal are common shapes of coordination
polyhedron.
53. What is meant by unidentate and bidentate ligands? Give two examples for each.
Unidentate or monodentate ligand: A molecule or an ion which has only one donor atom to form
one coordinate bond with the central metal ion is called unidentate ligand, e.g., Cl – and NH3.
Bidentate or didentate ligand: A molecule or an ion which contains two donor atoms and forms
two coordinate bonds with the central metal ion is called a bidentate ligand, e.g., ethane-1,2-
diamine (NH2—CH2—CH2—NH2) and oxalate (C2O42-).
54. Specify the oxidation numbers of the metals in the following coordination entities:
(i) [Co(H2O)(CN)(en)2]2+
x + (0) + (–1) + (0) =+ 2 or x = + 3
(ii) [CoBr2 (en)2] +
x + 2(–1) + 0 = + 1 or x = + 3
(iii) [PtCl4]2–
x – 4 = –2 or x = + 2

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(iv) K3[Fe(CN)6]
3(1) + x + 6 (–1) = 0 or x = + 3
(v) [Cr(NH3)3Cl3]
x + 0 + 3(–1) = 0 or x = + 3
55. Using IUPAC norms, write the formulae of the following:
(i) Tetrahydroxozincate(II) - [Zn(OH)4]2–
(ii) Potassium tetrachloridopalladate(II) - K2[PdCl4]
(iii) Diamminedichloridoplatinum(II) - [Pt(NH3)2Cl2]
(iv) Potassium tetracyanidonickelate(II) - K2[Ni(CN)4]
(v) Hexaammineplatinum(IV) - [Pt(NH3)6]4+
(vi) Tetrabromidocuprate(II) - [CuBr4]2–
(vii) Pentaamminenitrito-N-cobalt(III) - [Co(NH3)5(NO2)]2+
56. Using IUPAC norms, write the systematic names of the following:
(i) [Co(NH3)6]Cl3 - Hexaamminecobalt(III) chloride
(ii) [Pt(NH3)2Cl(NH2CH3)]Cl - Diamminechlorido(methylamine)platinum(II) chloride
(iii) [Ti(H2O)6]3+ - Hexaaquatitanium(III) ion
(iv) [Co(NH3)4Cl(NO2)]Cl - Tetraamminechloridonitrito-N-cobalt(III) chloride
2+
(v) [Mn(H2O)6] - Hexaaquamanganese(II) ion
(vi) [Ni(NH3)6]Cl2 - Hexaamminenickel(II) chloride
(vii) [Co(en)3]3+ - Tris(ethane-1, 2-diamine)cobalt(III) ion
57. How many geometrical isomers are possible in the following coordination entities?
(i) [Cr(C2O4)3]3– (ii) [Co(NH3)3Cl3]
(i) Geometrical isomers are not possible.
(ii) Two geometrical isomers are possible

58. List various types of isomerism possible for coordination compounds, giving an example of
each.

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 Solvate isomerism
(a) Structural isomerism:
(i) Linkage isomerism: This type of isomerism arises due to the presence of an ambidentate ligand in a
coordination compound. Example: [Co(NH3)5NO2]2+ and [Co(NH3)5 ONO]2+
(ii) Coordination isomerism: This type of isomerism arises due to interchange of ligands between the
cationic and anionic entities of different metal ions present in a complex. Example: [Co(NH3)6]
[Cr(CN)6] and [Cr(NH3)6] [Co(CN)6]
(iii) Ionisation isomerism: Ionisation isomerism arises when the counter ion in a complex salt is a
potential ligand and can displace a ligand which can then become the counter ion. Example:
[Co(NH3)5Cl]SO4 and [Co(NH3)5SO4] Cl
(iv) Solvate isomerism: They differ in number of solvent molecule is directly bonded to central metal
ion. If water is the solvent then this form of isomerism is known as ―hydrate isomerism‖. Example:
[Cr(H2O)6] Cl3 and [Cr(H2O)5Cl] Cl2. H2O
(b) Stereoisomerism: Stereoisomerism is of two types:
(i) Geometrical isomerism: This type of isomerism arises in heteroleptic complexes due to difference
in geometrical arrangement of the ligand around the central metal ion. If the same kind of ligand
occupy adjacent positions, the isomer is called cis, and if these are opposite to each other, the isomer is
called trans. Example: [Pt(NH3)2Cl2]

(ii) Optical isomerism: This type of isomerism is exhibited by chiral molecules. Optical isomers are
mirror images that cannot be superimposed on one another. These are called as enantiomers and rotate
the plane of polarised light equally but in opposite directions. The isomer which rotates the plane of
polarised light towards left is called laevorotatory (l) while which rotates the plane towards right is
called dextrorotatory (d). Example: [Cr(ox)3]3-

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59. Draw the structures of optical isomers of (i) [Cr(C2O4)3]3– (ii) [PtCl2(en)2]2+
(iii) [Cr(NH3)2Cl2(en)]+
(i) [Cr(C2O4)3]3–:

(ii) [PtCl2(en)2]2+:

(iii) [Cr(NH3)2Cl2(en)]+:
Cis [Cr(NH3)2Cl2(en)]+

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60. Draw all the isomers (geometrical and optical) of: (i) [CoCl2(en)2]+ (ii) [Co(NH3)Cl(en)2]2+
(iii) [Co(NH3)2Cl2(en)]+

61. Write all the geometrical isomers of [Pt(NH3)(Br)(Cl)(py)] and how many of these will
exhibit optical isomerism?

Square planar complexes do not show optical isomerism.

62. Aqueous copper sulphate solution (blue in colour) gives (i) a green precipitate with aqueous
potassium fluoride, and (ii) a bright green solution with aqueous potassium chloride. Explain
these experimental results.

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Aqueous copper sulphate exists as [Cu(H2O)4] SO4. The blue colour of the solution is due to
[Cu(H2O)4]2+ ions.
(i) [Cu(H2O)4]2+ + 4F- → [CuF4]2- + 4 H2O
(Blue) (green ppt)
(ii) [Cu(H2O)4]2+ + 4Cl- → [CuCl4]2- + 4 H2O
(Blue) (bright green)
63. What is the coordination entity formed when excess of aqueous KCN is added to an aqueous
solution of copper sulphate? Why is it that no precipitate of copper sulphide is obtained
when H2S(g) is passed through this solution?
[Cu(H2O)4]2+ + 4 CN- → K2 [Cu(CN)4]2- + 4 H2O
As CN– ions are strong ligands the complex is very stable. It is not replaced by S 2– ions when
H2S gas is passed through the solution and thus no precipitate of CuS is obtained.
64. Draw figure to show the splitting of d orbitals in an octahedral crystal field.

65. What is spectrochemical series? Explain the difference between a weak field ligand and a
strong field ligand.
The arrangement of ligands in order of their increasing field strengths, i.e., increasing crystal
field splitting energy (CFSE) values is called spectrochemical series.
I– < Br– < SCN– < Cl– < S2– < F– < OH– < C2O42– < H2O< NCS– < EDTA4 – < NH3< en< CN– < CO
The ligands with a small value of CFSE (Δo) are called weak field ligands whereas those with a
large value of CFSE are called strong field ligands.
66. What is crystal field splitting energy? How does the magnitude of Δo decide the actual
configuration of d-orbitals in a coordination entity?
When ligands approach a transition metal ion, the d-orbitals split into two sets, one with lower
energy and the other with higher energy. The difference of energy between the two sets of orbitals
(t2g and eg) is called crystal field splitting energy (Δo).
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(i) If Δ0 < P (pairing energy), the 4th electron enters one of the eg orbitals, and the
configuration will be t32g e1g, in case of weak field ligands and high spin complex will be
formed.
(ii) If Δ0 > P, the 4th electron pairs up in one of the t2g orbitals giving the configuration t42g e0g,
in case of strong field ligands and low spin complex will be formed.
67. [Cr(NH3)6]3+ is paramagnetic while [Ni(CN)4]2– is diamagnetic. Explain why.
Formation of [Cr(NH3)6]3+ :
Electronic configuration of Cr (Z=24) = [Ar] 3d5 4s1
The oxidation state of chromium in [Cr(NH3)6]3+ ion is +3.
Electronic configuration of Cr3+ = [Ar] 3d3 4s0

Hybridization: d2sp3
Geometry: octahedral, inner orbital complex, high spin complex.
Magnetic property: paramagnetic, due to the presence of 3 unpaired electrons.
The spin-only magnetic moment (μ) = 𝑛 (𝑛 + 2) = 3 (3 + 2) = 15 = 3.82 BM.
[Ni(CN)4]2–:
Electronic configuration of Ni (Z=28) = [Ar] 3d8 4s2
Nickel in [Ni(CN)4]2– is in the +2 oxidation state.
Electronic configuration of Ni2+ = [Ar] 3d8 4s0

CN- is a strong field ligand, so it causes pairing of electrons.

Hybridization: dsp2
Geometry: Square planar
Magnetic property: Since no unpaired electron is present, [Ni(CN)4]2– is diamagnetic.

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68. [Fe(CN)6]4– and [Fe(H2O)6]2+ are of different colours in dilute solutions. Why?
In both the complexes, Fe is in +2 oxidation state with d6 configuration. As the ligands CN- and
H2O possess different crystal field splitting energy (Δ0), they absorb different components of
visible light for d-d transition. Hence, the transmitted colours are different in dilute solutions.
69. Give the oxidation state, d orbital occupation and coordination number of the central metal
ion in the following complexes: (i) K3[Co(C2O4)3] (ii) cis-[Cr(en)2Cl2]Cl (iii) (NH4)2[CoF4] (iv)
[Mn(H2O)6]SO4

70. Write down the IUPAC name for each of the following complexes and indicate the oxidation
state, electronic configuration and coordination number. Also give stereochemistry and
magnetic moment of the complex: (i) K[Cr(H2O)2(C2O4)2].3H2O (ii) [Co(NH3)5Cl]Cl2
(iii) [CrCl3(py)3] (iv) Cs[FeCl4]
(i) K[Cr(H2O)2(C2O4)2].3H2O:
IUPAC name: Potassium diaquadioxalatochromate(III) trihydrate
Oxidation state of Cr = +3; coordination number = 6
Stereochemistry : octahedral
Electronic configuration of Cr3+: [Ar] 3d3 4s0= (t2g)3, (eg)0
The spin-only magnetic moment (μ) = 𝑛 (𝑛 + 2) = 3 (3 + 2) = 15 = 3.82 BM.
(ii) [Co(NH3)5Cl]Cl2:
IUPAC name: Pentaamminechloridocobalt(III) chloride
Oxidation state of Co = +3, coordination number = 6
Stereochemistry = octahedral
Electronic configuration of Co3+: [Ar] 3d6 4s0 = (t2g)6, (eg)0
Magnetic moment (µ) = 0
(iii) [CrCl3(py)3] :
IUPAC name: Trichloridotripyridinechromium(III)
Oxidation state of Cr = +3, coordination number = 6
Stereochemistry : octahedral
Electronic configuration of Cr3+: [Ar] 3d3 4s0= (t2g)3, (eg)0

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The spin-only magnetic moment (μ) = 𝑛 (𝑛 + 2) = 3 (3 + 2) = 15 = 3.82 BM.

(iv) Cs[FeCl4] :
IUPAC name: Caesium tetrachloridoferrate(III)
Oxidation state of Fe = +3; coordination number = 4
Stereochemistry = Tetrahedral
Electronic configuration of Fe3+: [Ar] 3d5 4s0 = (e)2, (t2)3
The spin-only magnetic moment (μ) = 𝑛 (𝑛 + 2) = 5 (5 + 2) = 35= 5.82 BM.
71. Explain the violet colour of the complex [Ti(H2O)6]3+ on the basis of crystal field theory.
Electronic configuration of Ti (Z=22) = [Ar] 3d2 4s2
Titanium in [Ti(H2O)6]3+ is in the +3 oxidation state.
Electronic configuration of Ti3+ = [Ar] 3d1 4s0
Due to the presence of one unpaired electron d−d transition occurs. The unpaired electron is
excited from the t2g to eg level by absorbing yellow light and emit violet colour. Hence the complex
appears violet.

72. Discuss briefly giving an example in each case, the role of coordination compounds in: (i)
analytical chemistry (ii) Medicinal Chemistry
(ii) In analytical chemistry:
 EDTA is used in the determination of hardness of water (estimation of Ca2+ and Mg2+).
Dimethyl glyoxime is used in the estimation of Ni2+.
 Detection of Cu2+ is based on the formation of a blue tetraammine copper (II) ion.
(iii)Medicinal Chemistry:
 Cisplatin [Pt(NH3)2Cl2], is used in the treatment of cancer.
 EDTA complex of calcium is used in the treatment of lead poisoning.
73. How many ions are produced from the complex, [Co(NH3)6]Cl2 in solution?
[Co(NH3)6]Cl2 → [Co(NH3)6]2+ + 2Cl-
Ans: 3 ions.
74. Amongst the following ions which one has the highest magnetic moment value?
(i) [Cr(H2O)6]3+ (ii) [Fe(H2O)6]2+ (iii) [Zn(H2O)6]2+
The oxidation states are: Cr (III), Fe (II) and Zn (II).
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EC of Cr3+ = 3d3, unpaired electrons = 3, μ = 𝑛 (𝑛 + 2) = 3 (3 + 2) = 15= 3.83 BM.

EC of Fe2+ = 3d6, unpaired electrons = 4 , μ = 𝑛 (𝑛 + 2) = 4 (4 + 2) = 24= 4.89 BM.

EC of Zn2+ = 3d10, unpaired electrons = 0, μ = 0
Ans: [Fe(H2O)6]2+
75. What will be the correct order for the wavelengths of absorption in the visible region for the
following: [Ni(NO2)6]4– , [Ni(NH3)6]2+ , [Ni(H2O)6]2+
As metal ion is fixed, the increasing CFSE values of the ligands from the spectrochemical
series are in the order:
H2O < NH3 < NO2 –
Hence, the energies absorbed for excitation will be in the order:
[Ni(H2O)6]2+ < [Ni(NH3)6]2+ < [Ni(NO2)6]4–
As E = hc / λ, therefore, the wavelengths absorbed will be in the opposite order,
[Ni(NO2)6]4– < [Ni(NH3)6]2+ < [Ni(H2O)6]2+
76. Why is CO a stronger ligand than Cl– ?
CO is a stronger ligand than Cl– as it is a π-acceptor ligand.
77. Using IUPAC norms write the formulae for the following:
(i) tris(ethane-1, 2-diamine) chromium (III) chloride
(i) [Cr(en)3]Cl3
78. When a coordination compound PtCl4.6NH3 is mixed with AgNO3, 4 moles of AgCl are
precipitated per mole of the compound. Write
(i) structural formula of the complex.
(ii) IUPAC name of the complex.
(i) [Pt(NH3)6]Cl4
(ii) hexaammineplatinum (IV) chloride
79. A chloride of fourth group cation in qualitative analysis gives a green coloured complex [A]
in aqueous solution which when treated with ethane-1, 2-diamine (en) gives pale-yellow
solution [B] which on subsequent addition of ethane-1, 2-diamine turns to blue/purple [C ]
and finally to violet [D]. Write the structures of complexes [A], [B], [C ] and [D].
A = [Ni(H2O)6]2+ B = [Ni(H2O)4 (en)]2+
C = [Ni(H2O)2(en)2]2+ D = [Ni(en)3]2+
80. Using IUPAC norms, write the formulae for the following complexes:
(i) hexaaquachromium (III) chloride
(ii) sodium trioxalatoferrate (III)
(i) [Cr(H2O)6]Cl3
(ii) Na3[Fe(C2O4)3]

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81. Write IUPAC name of the complex [Co(en)2(NO2)Cl]+. What type of structural isomerism is
shown by this complex?
Chloridobis-(ethane-1,2-diamine)nitrito-N-cobalt(III) ion. This complex shows linkage
isomerism.
82. Why do compounds having similar geometry have different magnetic moment?
It is due to the presence of weak and strong ligands in complexes, if CFSE is high, the complex
will show low value of magnetic moment and vice versa, e.g., [CoF6]3– and [Co(NH3)6]3+, the
former is paramagnetic and the latter is diamagnetic.
83. Write the correct formulae for the following coordination compounds:
(i) CrCl3.6H2O (violet with 3 chloride ions precipitated as AgCl)
(ii) CrCl3.6H2O (light green colour, with 2 chloride ions precipitated as AgCl )
(iii) CrCl3.6H2O (dark green colour, with 1 chloride ion precipitated as AgCl )
(i) [Cr(H2O)6]Cl3
(ii) [Cr(H2O)5Cl]Cl2.H2O
(iii) [Cr(H2O)4Cl2]Cl.2H2O
84. CO is a stronger complexing reagent than NH3- why?
CO has empty π-orbitals which overlap with filled d-orbitals (t2g orbitals) of transition metals
and form π -bonds by back bonding. These π -interactions increase the value of crystal field
stabilization energy (Δ0). As NH3 cannot form π- bonds by back bonding, therefore, CO is stronger
ligand than NH3.

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