Coordination Compounds

Vikas Edutech
Coordination compounds
Coordination compounds are those addition molecular compounds which retain their identity in solid
state as well as in dissolved state. In these compounds. the central metal atom or ion is linked by ions
or molecules with coordinate bonds. e.g., Potassium ferrocyanide, K4 [Fe(CN)6].
Coordinate bond
In this the shared pair is donated by only one atom and the one that donates is donor and the other
which accepts is acceptor.

Examples of Coordination compounds

Hemoglobin – coordination compound of iron (Fe)
Chlorophyll – coordination compound of magnesium (Mg)
Vitamin B12- coordination compound of cobalt (Co)

Coordination chemistry
The branch of inorganic chemistrywhich deals with the study of coordination compounds is called
coordination chemistry.

Double salt
Double salt is the association of many substances or we can say they mainly contain two salts in
equimolar concentration.
like Mohr’s salt FeSO4.(NH4)2SO4.6H2O
Potash alum K2SO4Al2 (SO4)3.24H2O etc.

Coordination compounds vs double salts

Coordination compounds Double salts

1. Coordination compounds exist in solid as 1. The double salts exist in solid state and in
well as aqueous state aqueous state they dissociate into ions .

2. The coordination compounds exist in 2. Double salts exist in their own valances.
extended Valency.

3. Their properties are different from their 3. Their properties are same as their
constituents. constituents.

4. They retain their identity in solution. 4. They loose their identity in solution.

Terminology
1. Ligands
2. Central metal atom or ion
3. Coordination number
4.Coordination entity
5. Coordination polyhedron
6. Oxidation number or oxidation state
7. Charge on complex ion
1. Ligands

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 They are donor atom may be single atom or group of atoms
They are negatively charged or neutral species with lone pair Br-,Cl- etc or neutral like NH3,NO,CO etc
They act as Lewis bases
We can also call ligands as nucleophile as they are nucleus loving
For example in complex: {Co(NH3)6}Cl3 in this NH3 is ligand

Types of ligands On the basis of charge present, ligands are of three types:
Anionic ligands: CN‒ (cyanide), NO2‒ (nitrito-N), NO3‒ (nitrito), X‒ (halido), etc.
Cationic ligands: NO2+ (nitrosonium), NO+ (nitronium), N2F5+ (Hydrazinium), etc.
Neutral ligands: NH3 (ammine), H2O (aqua), CO (carbonyl), etc.
Types of ligands On the basis of number of coordinating atoms
Monodentate: It is the ligand which has only one donor atom.
For example: X‒ (halido), NH3 (ammine), H2O (aqua), CN‒ (Cyanido) .
Didentate: It is the ligand which has two donor atoms.
For example: H2NCH2CH2NH2 (ethane-1, 2-diamine) and C2O42‒ (oxalate).
Polydentate: Ligand containing several donor sites are called polydentate. EDTA (Ethylene Diamine
tetracetato ion): It is a hexadentate ligand.
Denticity: The no. of coordinate bonds formed by ligand with CMA.
Flexidentate ligands
A ligand which show variable denticity is called flexidentate ligand.
For example:
In [Co(NH3)4CO3]Br CO3 is bidentate and in [Co(NH3)5CO3]Br CO32- is monodentate ligand
Chelation: The property of ligand to form ring with metal atom is chelation.
Chelating ligand: Ligand which form ring with metal atom is called chelating ligand.
Chelating ring: The ring formed by ligand with metal atom is called chelating ring.
Characters of chelates
1. Chelating ligands are more stable than unidentate ligand.
2. Greater is the denticity, stable is the complex.
3. Larger the groups of ligands, unstable is the complex.
Importance of chelates
1. Softening of hard water.
2. Separation of lanthanoids.
3. Detection of metal ions.
Ambidentate ligands
Unidentate ligands which have more than one coordinating atoms.

For eg. CN- and NC-, SCN- and NCS-

2. Central atom or ion

The atom or ion to which ligands are attached is called central metal atom or ion.
It is mostly d block element
It act as an acceptor as it has vacant d orbital
Due to accepting nature they act as Lewis acids
For example in complex: {Co(NH3)6}Cl3 in this Co is central metal atom

3. Coordination entity
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 A coordination entity constitutes a central metal atom or ion bonded to a fixed number of ions or
molecules. For example, [CoCl3 (NH3 )3 ] is a coordination entity in which the cobalt ion is surrounded
by three ammonia molecules and three chloride ions.
If it is positively charged then it is called as cationic entity and in case of negative charge it is anionic
entity or complex.
Example: [Co(NH3)6]3+ cationic entity [Ag (CN)6]- anionic entity
counter ion
The atom or group of atoms written outside bracket is called counter ion.
Example: in [Co(NH3)6].Cl3
Cl3 is a counter ion or the ionizable part when dissolved in water
If coordination sphere is with positive charge than counter ion is with negative charge or vice versa.

4. Coordination number
The total number of coordinate bonds formed by central metal atom with ligands.
For eg: [Ag(CN)2]- has coordination number 2.
2,4,6 coordination number is most common.

5. Oxidation number or oxidation state

The charge carried by central metal atom when ligands are attached with metal atom in complex.
[Cu(NH3)4]2+
Cu + 4x0 = 2+
Cu = 2+

6. Charge on complex ion

The charge carried by complex ion is the sum of charge carried by central metal atom and ligands.

Homoleptic complex and heteroleptic complex

Homoleptic complex: metal atom/ion is linked with one type of ligands
For eg. [Cu(NH3)4]2+
Heteroleptic complex: metal ion is surrounded by more than one type of ligands.
[Co(NH3)2Cl2]+

Rules for writing formula of coordination compound

(i) The cation is written first.
(ii) The formula for the entire coordination compound is enclosed in square brackets.
(iii) The ligands are written in alphabetical order.
(iv) Polydentate ligands are also written alphabetically. In the case of abbreviated ligand, the first letter
of the abbreviation is in the alphabetical order.
(v) There should be no space between the ligands and metal within a coordination sphere.
(vii) The charge is indicated outside the square brackets as a right superscript with the number before
the sign.

Rules for naming coordination compounds

1. The name of cation is formed first followed by the name of anion.
2. A complex cation by naming the ligands in alphabetical order of their names and then metal ion.
3. The name of negative ligands end with letter o, neutral ligands have no ending, positive ligands end
with ium.
4. A complex anion named by writting ligands followed by name of the metal ending with suffix- ate.
5. Oxidation state of CMA is written in roman numerals in [ ] bracket.
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 6. A non-ionic complex is named as one word.

Negative ligands
Anion Name
Cl- Chloride
F- Flurorido
Br- Bromide
I- Iodide
O2- Oxo
O22- Peroxo
OH- Hydroxo
S2- Sulphide
NH2- Imido
NH2- Amido
N3- Nitride
P3- Phosphide
CO32- Carbonato
C2O42- Oxalate
SO42- Sulphato
NO3- Nitrato
NO2- Nitrito-N
ONO- Nitrito-O
SO32- Sulphito
CH3COO- Acetate
CN- Cyano or cyanido
NC- Isocyano
SCN- Thicyanato-S
NCS- Isothiocyanto-N

Neutral ligands: These ligands are named as molecules.

ligand Name
C5H5N Pyridine(py)
P(C6H5)3 triphenylphosphene
H2NCSNH2 Thiourea
H2NCH2CH2NH2 Ethane-1,2-diamine
H2O Aqua
NH3 Ammine
CO Carbonyl
NO Nitrosyl
CS Thiocarbonyl
ethylenediamminetetraacetate Edta
H2NCH2CH2NHCH2CH2NH2 diethylenetriamine
CH3NH2 Methylamine
C2H5NH2 Ethylamine

Positive ligands:
NO2+ Nitronium
NO+ Nitrosonium
H2NNH3+ Hydrazinium

CMA in anionic complexes:

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 Fe- ferrate Co- Cobaltate
Ni- Nickelate Zn- Zincate
Hg- mercurate Mn- manganite
Pt- palatinate Ag- argentite
Cu- cooperate Au- aurrate
Cr- chromate Ir- iridate
Al-aluminate Sn- stannate
Pd- palladate

Q. Write the IUPAC name of

(a) [Co(NH3)6]Cl3 (b) [Cr(en)3]Cl3 (c) K3[Fe(C2O4)3]
(d) K3[Co(CN)5(NO)] (e) Na2[CrF4O] (f) Fe4[Fe(CN)6]3
(g) Li[AlH4] (h) [Pt(NH3)4Cl2][PtCl4]
Q. Write the formula of the compound
(a) hexaaquairon(II)sulphate (b) potassiumpentacyanonitrosylcobalt(III)
(c) potassiumtetrahydroxozincate(II) (d) potassiumtrioxalatoaluminate(III)

Isomerism in coordination compounds

Two or more compounds having same molecular formula but different structural or spatial
arrangements are called isomers a d the phenomenon is called isomerism.
There are two types of isomers:
(a) Structural isomers: The compounds which have same molecular formula but different structure is
called structural isomers. The type of structural isomers are
(i) Ionisation isomers: The compound which give different ions in the solution but have same
composition are called structural isomers.
For example: [Pt(NH3)4Cl2]SO4 and [Pt(NH3)4 SO4] Cl2
Tetraamminedichloridoplatinum(IV)sulphate give white ppt with BaCl2 but
Tetraamminesulphateoplatinum(IV)chloride give white ppt with AgNO3 solution.
(ii) Solvate or hydrate isomers: The compound which have same composition but different number
of solvent molecules present as ligands and free molecules in crystal lattice are called solvate isomers.
If solvent is water then isomers are called hydrate isomers.
[Cr(H2O)6]Cl3 has violet colour, [Cr(H2O)5Cl]Cl2.H2O has blue green colour, [Cr(H2O)4Cl2]Cl.2H2O has
dark green colour
(iii) Linkage isomers: These isomers occur in the compounds containing ambidentate ligands.
[Cr(H2O)5(SCN)]2+ and [Cr(H2O)5(NCS)]2+
(iv) Coordination isomers: The isomers in which both anionic and cationic complex have different
distribution of ligands in cation and anion.
[Co(NH3)6][Cr(CN)6] and [Cr(NH3)6][Co(CN)6]
(b) Stereo or space isomers: The compounds which have same molecular formula but different
positions and arrangements of ligands in space around the metal ion. These are of two types.
(i) Geometrical or cis trans isomers: Geometric isomers are two or more coordination
compounds which contain the same number and types of atoms, and bonds, but which have
different spatial arrangements of the atoms. This isomerism occur in heteroleptic complexes.
When a similar group is placed at an adjacent position the compound is named
with the prefix cis
When a similar group is placed at the opposite position the compound is named
with the prefix trans

A) Tetrahedral complexes: They do not show geometrical isomerism due to all four ligands
are equidistant to one another.
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 B) Square planar complexes:

Octahedral complexes

(ii) Optical isomers: Optical isomers rotate plane polarised light in opposite directions. These two isomers
are non-superimposable to each other and these molecules are called chiral. The name of these isomers
are dextro and leavo. Isomer which rotate plane polarised light into right is called dextro but isomer
which rotate that light in left is called leavo.

Effective Atomic number(EAN)

Sidgwick rule or Effective atomic number

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 Total number of electrons present in central metal atom or ion after accepting electron pairs from
ligands through coordinate bonds is called effective atomic number
K3[Fe(CN)6]
Atomic number of Fe = 26
Number of electrons in Fe3+ = 23
Electrons accepted from ligands = 12
Total number of electrons in Fe3+ in complex = 23+12 = 35

Werner theory of coordination compounds

Alfred Werner (1866-1919), a Swiss chemist was the first to formulate his ideas about the structures of
coordination compounds. He prepared and characterised a large number of coordination compounds
and studied their physical and chemical behaviour by simple experimental techniques.
Precipitation studies of cobalt chloride and ammonia
In a series of compounds of cobalt(III) chloride with ammonia, it was found that some of the chloride
ions could be precipitated as AgCl on adding excess silver nitrate solution in cold but some remained in
solution.
1 mol CoCl3 .6NH3 (Yellow) gave 3 mol AgCl
1 mol CoCl3 .5NH3 (Purple) gave 2 mol AgCl
1 mol CoCl3 .4NH3 (Green) gave 1 mol AgCl
1 mol CoCl3 .4NH3 (Violet) gave 1 mol AgCl
Molar conductivity of cobalt chloride and ammonia
By comparing the molar conductance of the compounds with some known electrolytes, werner was
able to predict the number of ions present in the solution.
For example: CoCl3 .6NH3 behaved as 1:3 electrolyte, CoCl3 .5NH3 behaved as 1:2 electrolyte,
CoCl3 .4NH3 behaved as 1:1 electrolyte.

Postulates of werner’s theory

(i) Metals have two types of valencies (or linkages) known as- (a) Primary or Principal or Ionisable
Valency and (b) Secondary or Auxiliary or Non-ionisable Valency.
(ii) In modern terminology, the primary valencies usually indicate the oxidation number of the metal
ion whereas secondary valencies represent the coordination number of the metal.
(iii) The primary valency of the central metal ion is always satisfied by anions and its attachment to the
metal is shown by dotted lines. The secondary valencies may be satisfied either by anions or by neutral
molecules and their attachment to the metal is shown by thick lines. For example- NH3 is added to
cobalt chloride, a complex CoCl3.6NH3 is obtained, in which primary valencies of Co are satisfied by
three chloride ions whereas the secondary valencies are satisfied by six NH3 molecules.
[Co(NH3)6]Cl3

(iv) The ions/groups bound by the secondary linkages to the metal have characteristic spatial
arrangements corresponding to different coordination numbers.
Coordination polyhedra

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 The spatial arrangement of the ligand atoms which are directly attached to the central atom/ion
defines polyhedron about the central atom/ion [Co(NH3)6]3+, [Ni (CO)4] and [Pt Cl4]2- are respectively
octahedral, tetrahedral and square planar coordination polyhedra.
Coordination polyhedral

Limitations of werner’s theory

It could not answer the following questions:
1. Why only certain elements form coordination compounds?
2. Why the coordination entity has a definite geometry?
3. Why do some compounds have definite magnetic and optical properties?

Bonding in coordination compounds

The two theories which explain bonding in coordination compounds are:
1. Valence bond theory
2. Crystal field theory
1. Valence bond theory
The basic assumptions of the theory are:
(a) The central metal atom in the complex must make available a number of empty orbitals equal to its
coordination number for accommodating the electrons from ligands.
(b) The appropriate atomic orbitals (s, p, d) of the metal hybridise to give a new set of equivalent
hybrid orbitals which are directed towards the ligand sites.
(c) The d orbitals used for hybridization may be either inner (n – 1)d orbitals or outer nd orbitals.
(d) The hybrid orbitals of the metal overlap with the filled orbitals of\the ligands to form coordinate
bonds.
TYPES OF HYBRIDIZATIONS AND GEOMETRIES IN COORDINATION COMPLEXES:
Hybridization Geometry Coord no.
sp3 Tetrahedral 4
dsp2 Square Planar 4
sp3d2 or d2sp3 Octahedral 6
dsp3 Trigonal Bipyramidal 5
sp3d Square Pyramidal 5
Octahedral entity (coord no. 6)
[Co(NH3)6]3+
All the electrons are paired therefore it is diamagnetic

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 [CoF6]3-
Complex has unpaired electrons, therefore, it will be paramagnetic in nature.
It is octahedral complex having coord no. 6

Square planar entity (4 ligands)

[Ni(CN)4]2-
All the electrons are paired therefore it is diamagnetic

[CoCI4]–

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 Since, complex has unpaired electrons. so it will be paramagnetic in nature.

Inner and outer orbital complexes

Inner Orbital Complexes: In inner orbital complexes, the d orbitals involved in the hybridization are
in a lower energy level than s and p orbitals. These are low spin complex.
Outer Orbital Complexes: Outer orbital complexes are composed of metal atoms that use outermost
shell d orbitals for the hybridization in the central metal atom. These are high spin complex.
Predicting the type of hybridisation from magnetic moment
If CMA has 3 or less unpaired electrons (Ti3+, V3+, Cr3+)for octahedral complex then hybridisation is
sp3d2.
If CMA has more than 3 unpaired electrons 4e-(Cr2+, Mn3+), 5e-(Mn2+, Fe3+), for octahedral complex
then hybridisation is d2sp3.
Predicting the geometry of a complex from its magnetic moment
[NiCl4]2- ion has two unpaired electrons hence the possible hybridisation is sp3 and geometry is
tetrahedral.
[Ni(CN)4]2- ion has no unpaired electrons hence the possible hybridisation is dsp2 and geometry is
square planar.
Predict the hybridisation, geometry, magnetic nature, magnetic moment of the following
complexes:
(a) [Cr(NH3)3]3+ -inner orbital
(b) [Fe(CN)6]3- inner
4-
(c) [Fe(CN)6] inner
3-
(d) [CoF6] outer
(e) [Fe(H2O)6]3+ outer
(f) [FeF6]4- outer
(g) [Mn(CN)6]3- inner
Limitations of VBT
1. It cannot explain why some complexes of a metal ion in a particular oxidation state is low spin while
in same oxidation state is high spin.
2. It could not explain the colour of complexes.
3. It could not distinguish strong ligand and weak ligand.
4. in some cases, experimental value of magnetic moment is different from that is calculated from VBT.
Important questions
1. Assertion : [Co(NH3)5SO4]Cl gives a white precipitate with silver nitrate solution.
Reason : The complex dissociates to give Cl– and SO42– ions.

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 (a) Both Assertion (A) and Reason (R) are true and Reason (R) is the correct explanation of the
Assertion (A).
(b) Both Assertion (A) and Reason (R) are true, but Reason (R) is not the correct explanation of the
Assertion (A).
(c) Assertion (A) is true, but Reason (R) is false.
(d) Assertion (A) is false, but Reason (R) is true. (2023)
2. One mole of CrCl3⋅6H2O compound reacts with excess AgNO3 solution to yield two moles of
AgCl(s) . The structural formula of the compound is
(a) [Cr(H2O)5Cl]Cl2⋅H2O (b) [Cr(H2O)3Cl3]⋅3H2O
(c) [Cr(H2O)4Cl2]Cl⋅2H2O (d) [Cr(H2O)6Cl3] (2020) VSA (1 mark)
3. When a coordination compound CrCl3⋅6H2O is mixed with AgNO3, 2 moles of AgCl are
precipitated per mole of the compound. Write structural formula of the complex. (AI 2019, 1/2,
Delhi 2016)
4. What is the difference between a complex and a double salt? (AI 2019)
5. When a coordination compound CoCl3⋅6NH3 is mixed with AgNO3, 3 moles of AgCl are
precipitated per mole of the compound. Write structural formula of the complex. (1/2, AI 2016)
6. The oxidation number of Co in [Co(en) 3] 2(SO4) 3 is
(a) +2 (b) +3 (c) +4 (d) +6 (2021C)
7. Which of the following ligands form a ‘chelate’ complex with metal ion ?
(a) H2O (b) CN– (c) C2O4 2– (d) Cl– (2021C)
8. The coordination number of Cr in [CrCl2(ox) 2] 3– is
(a) 6 (b) 5 (c) 4 (d) 3 (2021C)
9. The coordination number of ‘Co’ in the complex [Co(en) 3] 3+ is
(a) 3 (b) 6 (c) 4 (d) 5 (2020)
10. Assertion (A) : [Pt(en) 2Cl2] 2+ complex is less stable than [Pt(NH3)4Cl2]2+ complex. Reason (R) :
[Pt(en) 2Cl2]2+ complex shows chelate effect.
(a) Both Assertion (A) and Reason (R) are correct statements, and Reason (R) is the correct
explanation of the Assertion (A).
(b) Both Assertion (A) and Reason (R) are correct statements, but Reason (R) is not the correct
explanation of the Assertion (A).
(c) Assertion (A) is correct, but Reason (R) is incorrect statement.
(d) Assertion (A) is incorrect, but Reason (R) is correct statement. (2020)
11. The oxidation state of Ni in [Ni(CO)4] is
(a) 0 (b) 2 (c) 3 (d) 4 (2020)
3– 3+,
12. Amongst [Fe(C2O4) 3] and [Fe(NH3) 6] which is more stable and why? (2019C)
13. Write the coordination number and oxidation state of platinum in the complex [Pt(en)2Cl2].
(2018)
14. Which of the following is more stable complex and why? [Co(NH3)6]3+ and [Co(en)3]3+ (Delhi
2014)
15. The formula of the coordination compound tetraamminechloridonitrito-N-cobalt(III) chloride is
:
(a) [Co(NH3)4Cl(ONO)]Cl2 (b) [Co(NH3) 4Cl2(NO2)]Cl
(c) [Co(NH3)4Cl(NO2)]Cl (d) [Co(NH3) 4(NO2)]Cl3 (2021C) VSA (1 mark)
16. Write the formula of the following coordination compound : Iron(III)hexacyanidoferrate(II)
(1/3, 2018)
17. Write the IUPAC name of the following complex : [Cr(NH3)3Cl3]. (1/3, Delhi 2017)
18. Write the IUPAC name of the following complex : [Co(NH3)5(CO3)]Cl. (1/3, Delhi 2017)
19. When a coordination compound CrCl3⋅6H2O is mixed with AgNO3, 2 moles of AgCl are
precipitated per mole of the compound. Write IUPAC name of the complex. (1/2, Delhi 2016)
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 20. Give the formulae of the following compounds :
(a) Potassium tetrahydroxidozincate(II) (b) Hexaammineplatinum(IV) chloride
(2020)
21. Using IUPAC norms write the formulae for the following : (i) Pentaamminenitrito–O–cobalt(III)
chloride (ii) Potassium tetracyanidonickelate(II)
22. Using IUPAC norms write the formulae for the following : (a) Sodium dicyanidoaurate(I) (b)
Tetraamminechloridonitrito-N-platinum(IV) sulphate (AI 2017)
23. Using IUPAC norms write the formulae for the following : (a) Tris(ethane-
1,2,diamine)chromium(III) chloride (b) Potassium tetrahydroxozincate(II) (AI 2017)
24. Using IUPAC norms write the formulae for the following : (a) Potassium trioxalatoaluminate(III)
(b) Dichloridobis(ethane-1,2-diamine)cobalt(III) (AI 2017) Ap
25. (i) Write down the IUPAC name of the following complex : [Cr(NH3) 2Cl2(en)]Cl (en =
ethylenediamine) (ii) Write the formula for the following complex : Pentaamminenitrito-O-cobalt
(III). (Delhi 2015)
26. Using IUPAC norms write the formulae for the following coordination compounds : (i)
Hexaamminecobalt(III) chloride (ii) Potassium tetrachloridonickelate(II) (AI 2015)
27. (i) Write down the IUPAC name of the following complex : [Cr(en) 3]Cl3. (ii) Write the formula
for the following complex : Potassium trioxalatochromate(III). (Foreign 2015) SA II (3 marks)
28. (i) Write the IUPAC name of the following complex : [Co(NH3) 4(H2O)Cl]Cl2 (ii) What is the
difference between an Ambidentate ligand and a Bidentate ligand ? (iii) Out of [Fe(NH3) 6] 3+ and
[Fe(C2O4) 3] 3–, which complex is more stable and why? (Term II, 2021-22) U
29. Write the IUPAC name of the following : (i) [Co(NH3) 6]Cl3 (ii) [NiCl4] 2– (iii) K3[Fe(CN)6] (AI
2015C) Ap
30. Write down the IUPAC name for each of the following complexes : (i) [Co(NH3) 5Cl]Cl2 (ii)
K3[Fe(CN)6] (iii) [NiCl4] 2– (Delhi 2014C) U
31. Write the IUPAC name and draw the structure of each of the following complex entities : (i) Co
COO 3 3– COO (ii) [Cr(CO)6] (iii) [PtCl3(C2H4)]– (At. nos. Cr = 25, Co = 27, Pt = 78) (AI 2014C) Cr
32. The compounds [Co(SO4)(NH3) 5]Br and [Co(Br)(NH3) 5]SO4 represent
(a) optical isomerism (b) linkage isomerism
(c) ionisation isomerism (d) coordination isomerism. (2023)
33. The pair [Co(NH3) 4Cl2]Br2 and [Co(NH3) 4Br2]Cl2 will show
(a) linkage isomerism (b) hydrate isomerism
(c) ionization isomerism (d) coordinate isomerism (2020) U
34. Assertion (A) : Linkage isomerism arises in coordination compounds because of ambidentate
ligand.
Reason (R) : Ambidentate ligand like NO2 has two different donor atoms i.e., N and O.
(a) Both Assertion (A) and Reason (R) are correct statements, and Reason (R) is the correct
explanation of the Assertion (A).
(b) Both Assertion (A) and Reason (R) are correct statements, but Reason (R) is not the correct
explanation of the Assertion (A).
(c) Assertion (A) is correct, but Reason (R) is incorrect statement.
(d) Assertion (A) is incorrect, but Reason (R) is correct statement.
35. What type of isomerism is shown by the complex [Co(NH3) 5NO2]Cl2? (2020)
36. What type of isomerism is exhibited by the complex [Co(NH3) 5Cl]SO4? OR What type of
isomerism is exhibited by the following complex : [Co(NH3) 5SO4]Cl
37. What type of isomerism is shown by the complex [Co(NH3) 6][Cr(CN)6]?
38. What type of isomerism is shown by the complex [Co(NH3) 5(SCN)]2+?
39. What type of isomerism is exhibited by the complex [Co(NH3) 5NO2] 2+?

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 40. (a) Which of the following species cannot act as a ligand? Give reason. OH– , NH4 +, CH3NH2,
H2O (b) The complex [Co(NH3) 5(NO2)]Cl2 is red in colour. Give IUPAC name of its linkage isomer.
41. What type of isomerism is shown by the complex [Co(en) 2Cl2] +? Name the structure of an
isomer of this complex which is optically active. (1/2, 2020) An
42. What type of isomerism is shown by the complex [Co(en) 3]Cl3? (NCERT Intext, 1/3, Delhi
2017) OR What type of isomerism is exhibited by the complex [Co(en) 3] 3+? (en = ethane-1,2-
diamine) (1/3, AI 2014)
43. Draw one of the geometrical isomers of the complex [Pt(en) 2Cl2] 2+ which is optically active.
(1/3, Delhi 2016)
44. Draw one of the geometrical isomers of the complex [Pt(en) 2Cl2] 2+ which is optically inactive.
(AI 2016)
45. Draw the geometrical isomers of complex [Pt(NH3) 2Cl2]. (1/3, Delhi 2015)
46. Write down the IUPAC name of the complex [Pt(en) 2Cl2] 2+. What type of isomerism is shown
by this complex? (AI 2015)
47. Draw the geometrical isomers of complex [Pt(en) 2Cl2] 2+. (1/3, Foreign 2015) Cr SA I (2
marks)
48. Write IUPAC name of the complex [Pt(en) 2Cl2]. Draw structures of geometrical isomers for this
complex. (2019)
49. Write IUPAC name of the complex [Cr(NH3) 4Cl2] +. Draw structures of geometrical isomers
for this complex.
50. Indicate the types of isomerism exhibited by the following complexes : (i) [Co(NH3) 5(NO2)]2+
(ii) [Co(en) 3]Cl3 (en = ethylene diamine) (iii) [Pt(NH3) 2Cl2] (Delhi 2015C) U
51. Write the IUPAC name of the complex [Cr(NH3) 4Cl2] +. What type of isomerism does it exhibit?
(Delhi 2014)
52. Draw the structures of optical isomers of each of the following complex ions : [Cr(C2O4)]3–,
[PtCl2(en) 2] 2+, [Cr(NH3) 2Cl2(en)]+ (Delhi 2014C)
53. The magnetic moment of [NiCl4] 2– is (a) 1.82 B.M. (b) 2.82 B.M. (c) 4.42 B.M. (d) 5.46 B.M.
[Atomic number : Ni = 28]
54. Write the IUPAC name and hybridisation of the complex, [CoF6] 3–. (Given : Atomic number of
Co = 27) (1/2, 2020) OR Write the hybridisation and number of unpaired electrons in the complex
[CoF6] 3–. (Atomic no. of Co = 27) (1/3, 2018)
55. Predict the number of unpaired electrons in the square planar [Pt(CN)4] 2– ion. (2019C) An
56. Write the hybridisation and magnetic character of [Co(C2O4) 3] 3–. (At. no. of Co = 27) (1/3,
Delhi 2017)
57. Why is [NiCl4] 2– paramagnetic but [Ni(CO)4] is diamagnetic? (At. no. : Cr = 24, Co = 27, Ni =
28) (NCERT Intext, 1/3, AI 2014)
58. (i) Write the IUPAC name of [Mn(H2O)6]SO4. (ii) Why is [Fe(CN)6] 4– diamagnetic while [FeF6]
3– is paramagnetic ? [At. No. Fe= 26] (2021C)
59. Write IUPAC name and hybridization of the following complexes : (i) [Ni(CO)4] (ii) [CoF6] 3–
(Atomic number Ni = 28, Co = 27) (2020) Ap
60. (a) Write the IUPAC name and hybridisation of the complex [Fe(CN)6] 3–. (Given : Atomic
number of Fe = 26) (b) What is the difference between an ambidentate ligand and a chelating
ligand ? (2020) Ap
61. Out of [CoF6] 3– and [Co(en) 3] 3+, which one complex is (i) paramagnetic (ii) more stable (iii)
inner orbital complex and (iv) high spin complex (Atomic no. of Co = 27) (2019)
62. Out of [CoF6] 3– and [Co(C2O4) 3] 3–, which one complex is (i) diamagnetic (ii) more stable (iii)
outer orbital complex and (iv) low spin complex ? (Atomic no. of Co = 27) (Delhi 2019)
63. For the complex [Fe(H2O)6] 3+, write the hybridization, magnetic character and spin of the
complex. (At. number Fe = 26) (2/3,AI 2016)
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 64. Write the hybridization and shape of the following complexes : (i) [CoF6] 3– (ii) [Ni(CN)4] 2–
(Atomic number : Co = 27, Ni = 28) (AI 2015)
65. Write the state of hybridization, shape and IUPAC name of the complex [CoF6] 3–. (Atomic no.
of Co = 27) (Foreign 2014)
66. Write the state of hybridization, shape and IUPAC name of the complex [Ni(CN)4] 2–. (Atomic
no. of Ni = 28) (Foreign 2014)
67. Write the state of hybridization, shape and IUPAC name of the complex [Co(NH3) 6] 3+. (Atomic
no. of Co = 27) (Foreign 2014)
68. (a) On the basis of crystal field theory, write the electronic configuration for d4 with a strong
field ligand for which Do > P. (b) A solution of [Ni(H2O)6] 2+ is green but a solution of [Ni(CO)4] is
colourless. Explain. [Atomic number : Ni = 28] (2023)
69. (a) Write the hybridisation, shape and magnetic character of [CoF6] 3–. [Atomic number of Co =
27] (b) Write the formula of pentaamminechloridocobalt(III) chloride. (Term II, 2021-22) Ev
70. (i) Calculate the spin only magnetic moment of the complex [FeF6] 3–. (Atomic number of Fe =
26) (ii) Write the IUPAC name of the given complex : [Co(NH3) 5Cl]Cl2 (iii) Why is the complex
[Co(en) 3] 3+ more stable than [CoF6] 3– ? (Term II, 2021-22) Ev
71. (a) Using valence bond theory, predict the hybridization and magnetic character of the
complex : [Ni(CO)4] (Atomic number : Ni = 28) (b) Write IUPAC name of [Pt(NH3) 2Cl(NO2)]. (c)
Why [Co(en) 3] 3+ is a more stable complex than [Co(NH3) 6] 3+ ?
72. Write the hybridisation and magnetic character of the following complexes : (i) [Fe(H2O)6] 2+
(ii) [Ni(CN)4] 2– [Atomic number : Fe = 26, Ni = 28]
The following questions are case-based questions. Read the case carefully and answer the
questions that follow.
73. In coordination compounds, metals show two types of linkages, primary and secondary.
Primary valencies are ionisable and are satisfied by negatively charged ions. Secondary valencies
are non-ionisable and are satisfied by neutral or negative ions having lone pair of electrons.
Primary valencies are non-directional while secondary valencies decide the shape of the
complexes.
(i) If PtCl2.2NH3 does not react with AgNO3, what will be its formula?
(ii) What is the secondary valency of [Co(en)3] 3+?
(iii) (1) Write the formula of Iron(III)hexacyanidoferrate(II) (2) Write the IUPAC name of
[Co(NH3)5Cl]Cl2. OR
(iii) Write the hybridization and magnetic behaviour of [Ni(CN)4] 2–.

Crystal Field theory

This theory was developed by Hans Bethe and John Van Vleck.
1. The metal-ligand bond is ionic having electrostatic interactions similar to interactions between ions
in crystal, therefore this theory is named as Crystal Field theory. Negative ligand is anion and CMA is
cation.
If the ligand is neutral then it is polar and has negative end in dipole.
2. Each ligand is considered as a negative point and CMA is positive point.
The ligands around CMA are arranged in such a way that repulsion between them is minimum.
3. If the negative charge present near the CMA is symmetrical then all the five d orbitals have equal
energies i.e. they are degenerate.
If the negative charge present near the CMA is due to negative or neutral ligands then d orbitals split.
Crystal field theory for octahedral complexes
an octahedral coordination compound having six ligands surrounding the metal atom/ion, we observe
repulsion between the electrons in d orbitals and ligand electrons.

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 This repulsion is experienced more in the case of dx2-y2 and dz2 orbitals as they point towards the axes
along the direction of the ligand.
Hence, they have higher energy than average energy in the spherical crystal field.
On the other hand, dxy, dyz, and dxz orbitals experience lower repulsions as they are directed between the
axes.
Hence, these three orbitals have less energy than the average energy in the spherical crystal field.
Splitting of degenerate orbitals
Crystal field splitting
This splitting of degenerate level in the presence of ligand is known as crystal field splitting. The
difference between the energy of t2g and eg level is denoted by “Δo” (subscript o stands for octahedral).
Some ligands tend to produce strong fields thereby causing large crystal field splitting whereas some
ligands tend to produce weak fields thereby causing small crystal field splitting.
Thus, the repulsions in octahedral coordination compound yield two energy levels:
t2g– set of three orbitals (dxy, dyz and dxz) with lower energy
eg – set of two orbitals (dx2-y2 and dz2) with higher energy
Spectrochemical series

Strong field ligand and weak field ligand

The magnitude of crystal field splitting depends upon the field strength of the ligand and the charge on
the metal ion.
Ligands that cause only a small degree of crystal filed splitting (small value of Δo ) are termed as weak
field ligands, while ligands that cause a large splitting (large value of Δo)are called strong field
ligands.
Calculation of CFSE
Energy decreases by -0.4 Δo for each electron filled in t2g orbital.
Energy increases by 0.6 Δo for each electron filled in eg orbital.
For d1, d2 and d3 configuration filling occur in t2g only.
d1, CFSE = -0.4 Δo
d2, CFSE = 2(-0.4) = -0.8 Δo
d3, CFSE = 3(-0.4) = -1.2 Δo
For d4 configuration 3 electrons enter in t2g, 4th electron enters in t2g for low spin state and in eg for
high spin state.
Similarly for d5 and d6 configuration.
for d7, __ __ __ __
__ __ __ __ __ __
Low spin high spin
D8, d9 and d10 have only one arrangement and have fixed CFSE.
If Δo is large the low spin state is stable but of Δo is small, high spin state is more stable.
Pairing energy
The energy required for electron pairing in a single orbital is called pairing energy. It is denoted by P.
Comparison of Δo and P

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 If Δo < P 4th electron will enter eg and we get high spin complex. The ligands for which Δo < P are called
weak field ligands.
If Δo > P In d4, d5 and d6 pairing will occur in t2g and eg remains empty and we get low spin complex.
The ligands for which Δo > P are called strong field ligands.
D4 to d7 ions are more stable for strong field ligands.
Properties of the complexes
(a) Magnetism: If the electrons are paired, the complex is diamagnetic but if the electrons are
unpaired, the complex is paramagnetic.
(b) Colour of complexes

Transition metal atoms (or) ions with one (or) more unpaired electrons and their complexes exhibit
colour both in their solid and in solution states.
When light passes through a solution of the complex, the electron in the lower t2g level is promoted to a
higher eg level by absorbing light with energy equal to the energy difference between the t2g and
eg levels.
Colour of gemstones
The colour of gem stones like ruby and emerald is due to the d-to-d transition of electrons within the d
orbitals of the transition metal ion.
Ruby is a pink to blood red coloured gem stone of aluminium oxide.
Emerald is a green variety of beryl. The green colour of emerald is due to the presence of chromium
three plus ions.
In the absence of a ligand, crystal field splitting does not occur and the substance remains colourless.
CFT for tetrahedral complex
The four ligands approach the central metal atom along the direction of the leading diagonals from the
alternate corners of the cube.
In this field, the t2g orbitals (dxy , dyz and dzx) are pointing close to ligands than the ‘eg’ orbitals. (dx2
– y2 and dz2).
As a result, the energy of t2 orbitals increases by 0.4∆t and that of ‘e’ orbitals decreases by 0.6 ∆t.

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 CFT for square planar complex
Z components like dyz, dzx, dz2 are more stable. The lobes of dx2-y2 points toward ligands, this orbital
has high energy. Dyz and dzx are least in energy.

Factors affecting CFSE

1. oxidation state of metal ion: Higher the oxidation state larger the value of ∆.
2. Nature of metal ion.
3. Geometry of coordination entity: Value of ∆t =1/2 of ∆o.
4. Nature of ligand: strong field ligands and weak field ligands.
Limitations of CFT
1. only d orbitals are considered not s and p orbitals.
2. metal- ligand interaction is purely electrostatic is not realistic.
3. Ligand orbitals are not considered.

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