CHEMISTRY

COORDINATION COMPOUNDS
Co-ordination compounds are the complex compounds formed by the transition metals in
which the metal atoms are bond to a number of anions or neutral molecules.

Addition compound- Those compounds which are formed by the combination of 2 or more
stable compounds in stoichiometric ratio, are called addition compounds. They are of 2 types:-

1. Double salt: Those addition compounds which are stable in solid state, but they completely
dissociates in to ions in solution, are called Double salt.

Example: 𝐾2 𝑆𝑂4 . 𝐴𝑙2 (𝑆𝑂4 )3 . 24 𝐻2 𝑂 In Solution→ 2𝑘 + + 2𝐴𝑙 3+ + 2𝑆𝑂42−

(Potash alum)
𝐹𝑒𝑆𝑂4 (𝑁𝐻4 )2 𝑆𝑂4 . 6𝐻2 𝑂 In Solution → 2𝐹𝑒 2+ + 2𝑁𝐻4+ + 𝑆𝑂42−
(Mohr’s salt)

2. Coordination Compounds: Those compounds in which a metal atom is directly attached to a

no. of neutral molecule/ions are called coordination compounds and they retain their identity in
solid state as well as in solution is called coordination compound.
𝑖𝑛 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
Example: 𝐶𝑜𝐶𝑙3 + 6𝑁𝐻3 → [𝐶𝑜(𝑁𝐻3 )6 ]𝐶𝑙3 → [𝐶𝑜(𝑁𝐻3 )6 ]3+ + 3𝐶𝑙 −

WERNER’S THEORY OF COORDINATION COMPOUNDS

He proposed the concept of a primary valency and a secondary valency for a metal ion.

1. Metal atoms possess two types of valencies:

* Primary Valency
*Secondary Valency

2. They tend to satisfy both primary as well as secondary valency.

3. Primary valency is equal to the oxidation No. of central ion. It is ionisable. It is satisfied by
negative ions. e.g., In𝐶𝑟𝐶𝑙3 the primary valency is 3.

4. Secondary valency is equal to the co-ordination No. of central atom/ ion. It is directional and
non-ionisable. It is satisfied by neutral molecules or negative ions.

5. Metal atom has definite no. of secondary valencies and they are directed towards definite
position.

No. of secondary valency Arrangement

4 tetrahedral or square planar

6 octahedral

Example:[𝐶𝑜(𝑁𝐻3 )6 ]𝐶𝑙3
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*Primary valencies are non-directional while secondary valencies are directional.

SOME INPORTANT TERMS ABOUT COORDINATION COMPOUNDS

(A) Coordination sphere or coordination entity

It consists of central metal atom/ion and a definite no of neutral molecules and/or ions are
directly attached to it. Its formula is written in square bracket.

Coordination compound Coordination sphere/entity

1. [𝐶𝑂(𝑁𝐻3 )6 ]𝐶𝑙3 → [𝐶𝑜(𝑁𝐻3 )]3+ Cationic entity

2. 𝐾4 [𝐹𝑒(𝐶𝑁)6 ] → [𝐹𝑒(𝐶𝑁)6 ]4− Anionic entity

3. [𝑃𝑡(𝑁𝐻3 )2 𝐶𝑙2 ] → [𝑃𝑡(𝑁𝐻3 )2 𝐶𝑙2 ] Neutral entity

(B) Central Metal Atom/ion

The metal atom/ion to which a definite no. of neutral and/or ions are directly attached in
coordination entity are called central metal atom/ion

(C) Ligands
The neutral molecules and/ or ions which are directly attached to central metal atom/ion in
coordination entity are called ligands.

(D) Counter Ions

The ions which are represented outside the square bracket are called counter ions and they are
ionisable.

NOTE- According to valence bond theory metal-ligand bond is coordinated in which ligand is
donar and metal atom/ion is acceptor.

(E) Denticity of Ligands

The no. of donar sites/atoms present in a ligand is called its denticity.
On the basis of denticity ligands are of following types:-

(1) Monodentate ‘OR’ Unidentate ligands

Ligands having one coordinating site or donar site are called monodentate ligand. It forms one
sigma coordination bond with central metal atom.

Example:𝑁𝐻3 , 𝐻2 𝑂, 𝐶𝑁 − , 𝑁𝐶 − , 𝑂𝑁𝑂− , 𝑁𝑂2− , 𝑆𝐶𝑁 − , 𝑁𝐶𝑆 − , 𝐶𝑙 − , 𝐵𝑟 − , 𝐼 − , 𝐶𝑂 , 𝑒𝑡𝑐.

(2) Bidentate Ligands

The ligands having two donar sites are called bidentate ligand and it forms two coordinate
bonds with central metal atom/ion.

Example: 𝐶2 𝑂42− , 𝐻2 𝑁̈ − 𝐶𝐻2 − 𝐶𝐻2 − 𝑁̈𝐻2

Oxalate ion (ox) ethane-1,2diamine (en)

(3) Tridentate Ligands

The ligands having 3 donar sites are called tridentate ligands and they form 3 coordinate bonds
with central metal atom/ion.
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Example:𝐻2 𝑁̈ − 𝐶𝐻2 − 𝐶𝐻2 − 𝑁̈𝐻 − 𝐶𝐻2 − 𝐶𝐻2 − 𝑁̈𝐻2

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𝑁, 𝑁 ′ − 𝑏𝑖𝑠(2-aminoethyl) ethane,-1,2 diamine (dien)

(4) Hexadentate Ligands
A ligand having six donar sites are called hexadentate ligands and they form 6-coordinate bonds
with central metal atom/ion.

Example:𝐸𝐷𝑇𝐴4− (ethylene diamine tetracetate ion)

(5) Chelation
When a multidentate ligand form more than one sigma coordinate bond with central metal
atom/ion then a multimembered ring is formed which is called chelating ring. Such ligands are
called chelating ligand and the complex so formed is called chelating or metal chelate and this
property is called chelation.

Example:[𝑃𝑡(𝑒𝑛)2 ]2+

IMPORTANT USES OF CHELATE

1. Softening of hard water.

2. In the separation of lanthanoids and actinoids.
3. In the elimination of harmful radioactive metal from our body. We use 𝐸𝐷𝑇𝐴4− in this field.
4. In estimating some metal ions like 𝐶𝑢2+ , 𝑁𝑖 2+ , 𝑀𝑔2+ , 𝑒𝑡𝑐.

NOTE 1: The complex containing chelting ring are more stable than the complex containing
monodentate ligands, this is known 𝑎𝑠 𝑐ℎ𝑒𝑙𝑎𝑡𝑒 effect.

NOTE 2: Polydentateligands havehexadentate character, i.e. it is not necessary that all the donar
atom of polydentate ligand should form coordinate bond with central atom/ion.

Example: 𝐸𝐷𝑇𝐴4− which is a hexadentate ligand can also act as penta or tetra dentate ligand.

(6) Ambidentate Ligand

A monodentate ligand which can attach to central metal atom through different donar atom is
called ambidentate ligand.
‘OR’
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A mono dentate ligand having more than one coordinating atom/site is called ambidentate
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ligand.
Example: 𝑁𝑂2− , 𝐶𝑁 − , 𝑆𝐶𝑁 −

(i). 𝑁𝑂2− can attach either through Nitrogen or through oxygen.

𝑁𝑂2− (Nitro ion) 𝑂𝑁𝑂 − (Nitrite ion)

Through Nitrogen through Oxygen

(ii). 𝐶𝑁 − can attach either through Oxygen or through Nitrogen.

𝐶𝑁 − (Cyanide ion) 𝑁𝐶 − (Isocyanide ion)

Through Carbon through Nitrogen

(iii). 𝑆𝐶𝑁 − can attach either through sulphur or through Nitrogen:

𝑆𝐶𝑁 − (thiocyanide ion) 𝑁𝐶𝑆 − (thioisocyanide ion)

Through ‘S’ Through ‘N’

(7) Coordination Polyhedron

The spatial (in space) arrangement of ligands around central metal atom is called coordination
polyhedron. The most common co-ordination polyhedral are octahedral, square planar and
tetrahedral.

(8) Coordination Number

The number of sigma coordinate bond present between central metal atom/ion and ligands are
called coordination no. of central metal atom/ion.

Complex Compound Coordination no. of central metal atom/ion

[𝐶𝑜(𝑁𝐻3 )6 ]𝐶𝑙3 6

[𝑃𝑡 (𝑁𝐻2 )2 𝐶𝑙2 ] 4

[𝐶𝑟 (𝑂𝑋)3 ]3− 6

(9) Oxidation Number

Oxidation no. of central metal atom is defined as the charge which it would carry when all other
ions and molecules are moved from it.

Complex Compound Oxidation No. of Central metal atom

[𝐶𝑜(𝑁𝐻3 )6 ]𝐶𝑙3 +3
𝑋 + 0 − 3 ⇒ 𝑋 = +3

[𝐶𝑟(𝑂𝑋)3 ]3− +3
𝑋 − 6 = −3 ⇒ 𝑋 = +3

[𝑃𝑡(𝑁𝐻3 )𝐶𝑙2 ] +2
𝑋 + 0 − 2 = 0 ⇒ 𝑋 = +2

[𝑁𝑖(𝐶𝑂)4 ] 0
𝑋+0=0⇒𝑋 =0
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(10) Homolepticandheteroleptic Complexes
The complexes in which central metal atom is attached to one type of ligands are called
homoleptic complexes.

Example: [𝐶𝑜(𝑁𝐻3 )6 ]𝐶𝑙3

The complex in which central metal atom/ion is attached to more than one type of ligands are
called heteroleptic complex.

Example: [𝑃𝑡(𝑁𝐻3 )6 𝐶𝑙2 ]

[𝐶𝑜 (𝑁𝐻3 )4 𝐶𝑙2 ]𝐵𝑟

1) Mononuclear andPolynuclear Complexes

The complexes having only one central metal atom/ion are called mononuclear complexes.

Example: [𝐶𝑜(𝑁𝐻3 )6 ]𝐶𝑙3

and
The complexes having more than one central metal atoms/ions in the coordination entity such
complexes are called Polynuclear Complexes.

Example:

RULES FOR IUPAC NOMENCLATURE OF COORDINATION COMPOUNDS

1. First the name of cation is written whether it is complex or not.

2. The name of complex is written as one word

3. In the naming of complex, first the name of ligands are written in alphabetical order of their
names and then the name of central metal atom is written.

4. The oxidation state of central metal atom is written in Roman numbers in parenthesis (small
bracket)

5. If same type of ligand is present more than one time then the prefixes, di, tri, tetra, penta,
hexa…… etc are used before its name but if the name of ligand itself contain any of these prefixes
then bis, tris, tetrakis, pentakis……. etc are used before its name.

6. Any of the above prefixes are not used while deciding the alphabetical order.

7. If complex is anionic then the suffix-ate is used after the name of central metal atom, but if
complex is cationic or neutral then no suffix is added after the name of central metal atom.

8. The prefixes di, tri, tetra, are not used for counter ions and also no change is done in their
names.
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9. Name of anionic ligands ends with𝑂(𝑖𝑒−′ 𝑒 ′ 𝑖𝑠 replaced by O).

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Anionic Ligands Name

𝐶𝑙 − Chlorido
𝐵𝑟 − bromido
𝐼− Iodido
𝑂𝐻 − Hydroxido
𝐶𝑁 − Cyanido
𝑁𝐶 − isocyanido
𝑆𝐶𝑁 − thiocyanito
𝑁𝐶𝑆 − isothiocyanito
𝑁𝑂2− nitro or Nitrito-N
𝑂𝑁𝑂 − nitrito, or Nitrito-O-or Nitro-O-
𝑆 2− Sulphido
𝑆𝑂42− Sulphato
𝑆𝑂32− Sulphito
𝐶𝑂32− Carbonato
𝐻− Hydrido
𝐻2 𝑁 − 𝐶𝐻2 − 𝐶𝑂𝑂− Glycinato

Name of Some Neutral Ligands

𝑁𝐻3 ammine
𝐻2 𝑂 aqua
𝐶𝑂 carbonyl
𝑁𝑂 nitrosyl
𝑁̈𝐻2 − 𝐶𝐻2 − 𝐶𝐻2 − 𝑁̈𝐻2 (𝑒𝑛) → 𝑒𝑡ℎ𝑎𝑛𝑒 − 1,2– 𝑑𝑖𝑎𝑚𝑖𝑛𝑒
𝐶2 𝐻5 𝑁̈ (𝑃𝑦) Pyridine
𝐶𝐻3 𝑁̈𝐻2 methane amine
(𝐶6 𝐻5 )3 𝑃 triphenyl phosphine

SOME EXAMPLES OF NAMING

1. [𝐶𝑜(𝑁𝐻3 )6 ]𝐶𝑙3 → hexammine cobalt (III) Chloride

2. 𝐾4 [𝐹𝑒(𝐶𝑁)6 ] → potassium hexacyanido ferrate (II)
3. [𝐶𝑜(𝑁𝐻3 )6 ]3+ [𝐶𝑟(𝐶𝑁)6 ]3− → hexammine cobalt (III) hexacynaido chromate (III)
4. [𝐴𝑔(𝑁𝐻3 )2 ][𝐴𝑔(𝐶𝑁)2 ] → diammine silver (I) dicyanidoargentate (I)
5. [𝐶𝑜𝐶𝑙2 (𝑒𝑛)2 ]𝐶𝑙 → Dichloridobis-(ethane-1,2-diammine)cobalt (III) chloride

IUPAC RULES FOR FORMULA WRITING OF MONONUCLEAR COORDINATION

COMPOUNDS

1. First the formula of cation is written whether it is complex or not.

2. The formula of complex is written in square bracket.

3. In the formula of complex first the symbol of central metal atom/ion is written and then the
formula of ligands is written in alphabetical order of their name.

4. The formula of polyatomic ligand is written in parenthesis.

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5. In case of neutral coordinate compound the charge of cations is balanced by charge of anions.
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 In case of ionic complex entity charge is written outside square bracket as superscript.
Example: [𝐶𝑜(𝐶𝑁)6 ]3− , [𝐶𝑟(𝐻2 𝑂)6 ]3+ , 𝑒𝑡𝑐.

Example: Tetrammine aquaflorido cobalt (III) Bromide

[𝐶𝑜(𝑁𝐻3 )4 (𝐻2 𝑂)𝐹] 𝐵𝑟2

ISOMERISM IN COORDINATION COMPOUNDS

Isomerism in coordination compounds are of 2 types:-
(A) Structural isomerism
(B) Stereo Isomerism

(A) STRUCTURAL ISOMERISM

The coordination compounds having same molecular formula but different structures are called
structural isomers. This phenomenon is known as Structural isomerism.

Structural Isomerism are of 4 types:

1. Ionisation Isomerism
The coordination compounds having same molecular formula but which produce different ions
in solution are called ionisation isomers and this phenomenon is known as ionisation
isomerism.

Ionisation isomerism arises when the counter ions is itself is a potential ligand and thus can
displace a ligand which then can act as counter ion.

Example:[𝐶𝑜(𝑁𝐻3 )5 (𝑆𝑂4 )]𝐵𝑟 and [𝐶𝑜(𝑁𝐻3 )5 𝐵𝑟]𝑆𝑂4 are ionisation isomers of each other.

[𝐶𝑜(𝑁𝐻3 )5 (𝑆𝑂4 )]𝐵𝑟 → 𝑝𝑒𝑛𝑡𝑎𝑚𝑚𝑖𝑛𝑒𝑠𝑢𝑙𝑝ℎ𝑎𝑡𝑜𝑐𝑜𝑏𝑎𝑙𝑡(𝐼𝐼𝐼)𝑏𝑟𝑜𝑚𝑖𝑑𝑒

[𝐶𝑜(𝑁𝐻3 )5 𝐵𝑟](𝑆𝑂4 ) → 𝑝𝑒𝑛𝑡𝑎𝑚𝑚𝑖𝑛𝑒𝑏𝑟𝑜𝑚𝑖𝑑𝑜𝑐𝑜𝑏𝑎𝑙𝑡(𝐼𝐼𝐼)𝑠𝑢𝑙𝑝ℎ𝑎𝑡𝑒

2. Linkage Isomerism
In linkage isomerism ambidentate ligand is attach to central metal atoms through different
donar atoms.

Linkage isomerism arises in the coordination compounds containing ambidentate ligand.

Example:[𝐶𝑜(𝑁𝐻3 )5 (𝑁𝑂2 )]𝐶𝑙2 and [𝐶𝑜(𝑁𝐻3 )5 𝑂𝑁𝑂]𝐶𝑙2 are linkage isomers of each other.

[𝐶𝑜(𝑁𝐻3 )5 (𝑁𝑂2 )]𝐶𝑙2 → 𝑝𝑒𝑛𝑡𝑎𝑚𝑚𝑖𝑛𝑒𝑛𝑖𝑡𝑟𝑖𝑡𝑜 − 𝑁 − 𝐶𝑜𝑏𝑎𝑙𝑡(𝐼𝐼𝐼)𝐶ℎ𝑙𝑜𝑟𝑖𝑑𝑒

[𝐶𝑜(𝑁𝐻3 )5 𝑂𝑁𝑂]𝐶𝑙2 → 𝑝𝑒𝑛𝑡𝑎𝑚𝑚𝑖𝑛𝑒𝑛𝑖𝑡𝑟𝑖𝑡𝑜 − 𝑂 − 𝐶𝑜𝑏𝑎𝑙𝑡(𝐼𝐼𝐼)𝐶ℎ𝑙𝑜𝑟𝑖𝑑𝑒

3. Coordination Isomerism
In coordination isomerism the interchange of ligands between cationic and anionic entity takes
place.

It arises when both cation and anion are complex.

Example:[𝐶𝑜(𝑁𝐻3 )6 ][𝐶𝑟(𝐶𝑁)6 ] → ℎ𝑒𝑥𝑎𝑚𝑚𝑖𝑛𝑒𝑐𝑜𝑏𝑎𝑙𝑡(𝐼𝐼𝐼)ℎ𝑒𝑥𝑎𝑐𝑦𝑎𝑛𝑖𝑑𝑜𝑐ℎ𝑟𝑜𝑚𝑎𝑡𝑒

[𝐶𝑟(𝑁𝐻3 )6 ][𝐶𝑜(𝐶𝑁)6 ] → ℎ𝑒𝑥𝑎𝑚𝑚𝑖𝑛𝑒𝑐ℎ𝑟𝑜𝑚𝑖𝑢𝑚(𝐼𝐼𝐼)ℎ𝑒𝑥𝑎𝑐𝑦𝑎𝑛𝑖𝑑𝑜𝑐𝑜𝑏𝑎𝑙𝑡𝑎𝑡𝑒

4. Solvate Isomerism
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The coordination compound having same molecular formula but which differs in distribution of
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solvent molecule as ligand and as free-solvent molecule are called solvate isomers.
When Solvent molecules are water molecules then this isomerism is known as hydrate
isomerism.

Example:[𝐶𝑟(𝐻2 𝑂)6 ]𝐶𝑙3 → ℎ𝑒𝑥𝑎𝑞𝑢𝑎𝑐ℎ𝑟𝑜𝑚𝑖𝑢𝑚(𝐼𝐼𝐼)𝑐ℎ𝑙𝑜𝑟𝑖𝑑𝑒

[𝐶𝑟(𝐻2 𝑂)5 𝐶𝑙]𝐶𝑙2 𝐻2 𝑂 → 𝑝𝑒𝑛𝑡𝑎𝑞𝑢𝑎𝑐ℎ𝑜𝑟𝑖𝑑𝑜𝑐ℎ𝑟𝑜𝑚𝑖𝑢𝑚(𝐼𝐼𝐼)𝑐ℎ𝑙𝑜𝑟𝑖𝑑𝑒𝑚𝑜𝑛𝑜ℎ𝑦𝑑𝑟𝑎𝑡𝑒

(B) STEREOISOMERISM

The coordination compound having same molecular formula but different arrangement in space
of ligands around central metal atom/ion, are called stereo isomers and this phenomenon
known as stereoisomerism.

Stereo Isomerism is of two types:-

1. Geometrical Isomerism
2. Optical Isomerism

1. Geometrical Isomerism
Geometrical Isomerism isof two types

(A) Cis Isomer

When same types of ligands are present at adjacent corners then it is called cis isomers.

(B) Trans Isomer

When same types of ligand are present at opposite corners then it is called trans isomerism.

Examples
1.[𝑀𝑎2 𝑏2 ]type of complex/isomer
Example: → [𝑃𝑡(𝑁𝐻3 )2 𝐶𝑙2 ]

2. [𝑀𝑎2 𝑏𝑐]type of complex

Example:→ [𝑃𝑡(𝑁𝐻3 )2 𝐵𝑟 𝐶𝑙]
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3. [𝑀𝑎𝑏𝑐𝑑]type of complexes.
This type of complex shows three isomers two Cis and one trans.
Example:→ [𝑃𝑡(𝑁𝐻3 )𝐵𝑟𝐶𝑙(𝑃𝑦)]

In Cis isomer ligands of higher priority are at adjacent corners and in trans isomer ligands of
higher priority are at opposite corners.
The order of priority determined by CIP rule according towhich higher the atomic no. of atom
directly attach to central ion, the higher will be its priority or priority of ligand.

If same atoms are directly attach then we will consider atomic no. of next bonded atom.

Note: 1. Geometrical isomerism is not shown by tetrahedral complexes (Coordination no.→

4)Because in tetrahedral complexes all 4 corners are equivalent.

Note: 2. Geometrical Isomerism is not shown by homoleptic complexes.

4. [𝑀𝑎2 𝑏4 ] type complexes.

Example:→ [𝐶𝑜(𝑁𝐻3 )4 𝐶𝑙2 ]+

5. [𝑀𝑎2 𝑏2 (𝑒𝑛)] type of complexes

Example:→ [𝐶𝑜(𝑁𝐻3 )2 𝐶𝑙2 𝑒𝑛]+
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6. [𝑀𝑎2 (𝑒𝑛)2 ] type complexes
Example: [𝐶𝑜𝐶𝑙2 (𝑒𝑛)2 ]+type

7. [𝑀𝑎3 𝑏3 ] type
Example: [𝐶𝑜(𝑁𝐻3 )3 (𝑁𝑂2 )3 ]

(i) Whenthree same ligands are occupying adjacent position in the polyhedra is known as facial
(fac) isomers.
(ii) When three same ligands are occupying position around the meridian of the octahedral it is
known as meridional (mer) isomers.

2. Optical Isomerism ‘Or’ Enantiomer’s

A pair of compounds which are non-super imposable mirror images of each other are called
enantiomers or optical isomers.
Enantiomers are optically active i.e. they rotate the plan of polarised light. The enantiomers
which rotate the plane of polarised light in clockwise direction are called Dextrorotatory (‘d’ or
‘+’) and the enantiomers which rotate the plan of polarised light in anticlockwise direction
called Laevorotatory (‘𝑙’ or ‘-‘ )

Example:[𝐶𝑜𝐶𝑙2 (𝑒𝑛)2 ]+
1.
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They are not enantiomers as they are superimpose mirror images and will be optically inactive.

Example:[𝐶𝑜(𝑁𝐻3 )2 𝐶𝑙2 (𝑒𝑛)]3+

They are not enantiomer/optically

inactive.
BONDING IN COORDINATION
COMPOUNDS
Following theories were proposed to explain the bonding in coordination compounds.
(a) Werner’s Theory
(b) Valence Bond theory (VBT)
(c) Crystal field theory (CFT)
(d) Ligand field theory (LFT)

(B) Valence Bond Theory

This theory was proposed by L. Pauling. The main points of this theory are:-

1. Metal ligand bond is coordinate bond in which ligand is donar and metal atom is acceptor.

2. To accommodate electron pairs donated by ligand metal atom should possess requisite no. of
vacant orbitals of equal energies.

3. Thus empty orbitals of central metal atom/ion undergo hybridisation. The no. of empty
orbital which undergo hybridisation is equal to the coordinate number of central metal
atom/ion in complex.

4. If (n-1)d orbitals are used in hybridisation then the compound is called inner orbital complex
or low spin complex. If nd orbitals are used in hybridisation then complex is called outer orbital
complex or high spin complex.

5. If complex contain unpaired electron then it will be paramagnetic while if allelectrons are
paired then it is diamagnetic in nature.

6. The geometry of complex is determined by the type of hybridisation.

Type of Hybridisation Geometry of complex
𝑠𝑝3 tetrahedral
𝑑𝑠𝑝2 square planer
3 3
𝑠𝑝 𝑑 𝑜𝑟 𝑑𝑠𝑝 trigonal bipyramidal
𝑠𝑝3 𝑑2 𝑜𝑟 𝑑2 𝑠𝑝3 Octahedral

Note: In presence of strong field ligand like 𝑁𝐻3 , 𝑒𝑛, 𝐶𝑁 − , 𝐶𝑂, 𝑎𝑛𝑑 𝐶2 𝑂42− pairing of 𝑒 − in
(n-1)d orbitals of central metal atom takes place.

Examples:
1. [𝑁𝑖𝐶𝑙4 ]2−
𝑋 − 4 = −2
𝑋 = +2
𝑁𝑖 → 1𝑠 2 2𝑠 2 2𝑝6 3𝑠 2 3𝑝6 4𝑠 2 3𝑑8
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𝑁𝑖 2+ → 1𝑠 2 2𝑠 2 2𝑝6 3𝑠 2 3𝑝6 3𝑑8

Geometry → tetrahedral
Hybridisation → 𝑆𝑝3
Magnetic Properties → paramagnetic
It is neither inner orbital nor outer orbital complex. (i.e. (n-1)d or nd orbitals all not used)

2. [𝑁𝑖(𝐶𝑁)4 ]2−
𝑁𝑖 2+ → 1𝑠 2 2𝑠 2 2𝑝6 3𝑠 2 3𝑝6 3𝑑8 4𝑠 0 4𝑝0

Geometry → Square planar

Hybridisation → 𝑑𝑠𝑝2
Magnetic Properties→ diamagnetic
It is inner orbital complex (i.e. (n-1)d orbitals are used)

3. [𝐶𝑜(𝑁𝐻3 )6 ]3+
𝐶𝑜 3+ → 1𝑠 2 2𝑠 2 2𝑝6 3𝑠 2 3𝑝6 3𝑑6 4𝑠 0 4𝑝0

Geometry → octahedral
Hybridisation → 𝑑2 𝑆𝑝3
Magnetic Properties→ diamagnetic
It is inner orbitals complex.

4. [𝐹𝑒 𝐹6 ]3−
𝐹𝑒 3+ → 1𝑠 2 2𝑠 2 2𝑝6 3𝑠 2 3𝑝6 3𝑑5
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Geometry → octahedral
Hybridisation → 𝑠𝑝3 𝑑2
Magnetic Behaviour → paramagnetic
It is outer orbital complex.

5. [𝐶𝑜(𝐶2 𝑂4 )3 ]3−
𝐶𝑜 3+ → 1𝑠 2 2𝑠 2 2𝑝6 3𝑠 2 3𝑝6 3𝑑6 4𝑠 0 4𝑝0 4𝑑0
It is extra field ligand

Geometry→ octahedral
Hybridisation → 𝑑2 𝑆𝑝3
Magnetic Prop → Diamagnetic
It is inner orbital complex.

Limitations of valence Bond theory

1. It involves a no. of assumptions.
2. It does not explain colour exhibited by the coordination compounds.
3. It does not distinguish between weak field and strong field ligand.
4. It does not give exact prediction about tetrahedral and square planar structure of ‘4’
Coordination no. complexes.
5. It does not give quantitative interpretation of thermodynamic and kinetic stabilities of
coordination compound.

(B) CRYSTAL FIELD THEORY

This theory was proposed by bethe and vleck . The main points of this theory are:-
1. This theory consider metal ligand bond to be purely ionic which is form due to electrostatic
attraction between metal ion and ligands.

2. This theory considers anionic ligand as a point of negative charge and neutral ligand as a
dipole and in case of neutral molecule its negative pole shows electrostatic attraction with metal
ion.

3. According to this theory in the free state of metal ion all the five, d-orbitals are degenerate i.e.
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of equal energy. This degeneracy is maintain when –ve charge is applied around metal ion in
from of spherically symmetric field.
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4. But negative field applied by ligands i.e. when ligands approached metal ion then the five, d-
orbitals split into different energy sets this is called splitting of d-orbitals.

5. The pattern of splitting of d-orbitals depends upon the nature of crystal field applied by
ligands i.e. arrangement of ligand around metal ion.

Splitting of d-orbitals in octahedral Crystal field

Note: Reason
In octahedral arrangement ligands are supposed to approach central metal ion along x, y and z
axis. Thus the orbitals which lies on axis 𝑑𝑥 2 − 𝑦 2 and𝑑𝑧 2 suffers more repulsion and their
energy is increased by more, while the orbitals which lie in between axis (dxy, dyz, dxz) suffers
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less repulsion and thus their energy is less.

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Splitting of d-orbitals in tetrahedral
Crystal field

CRYSTAL FIELD SPLITTING ENERGY

(CFSE), ∆
The difference in energies of two orbital sets is called crystal field splitting energy.

The value of crystal field splitting energy for same metal ion depends upon nature of ligands.

Weak field and strong field Ligand

Those ligand which produce weak field are called weak field ligand. For such ligands value of
CFSE(∆) is low while those ligands which produce strong field ligand, result in great splitting
effect. That is for them the value of CFSE(∆) is high, such ligands are called strong field ligands.

Spectrochemical Series
When different ligands are arranged in increasing order of their field strength. Then such
arrangement is called spectrochemical series.

→ 𝐼 − < 𝐵𝑟 − < 𝑆𝐶𝑁 − < 𝐶𝑙 − < 𝑆 2− < 𝐹 − < 𝑂𝐻 − < 𝐶2 𝑂42− < 𝐻2 𝑂 < 𝑁𝐶𝑆 − < 𝐸𝐷𝑇𝐴4− < 𝑁𝐻3 <
𝑒𝑛 < 𝑁𝑂2− < 𝐶𝑁 − < 𝐶𝑂

Explanation of some properties of coordination compounds

1. Stability of low spin and high spin complexes

This electronic configuration in d-orbitals of central metal ion depends upon following 2
factors:-
(A) CFSE(∆)
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(B) Pairing energy (p)→The amount of energy require for the pairing of electron in an atomic
orbital is called pairing energy.
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Case:1 In case of strong field ligand. ∆> 𝑃,Thus the electron will pair up in lower energy d-
orbital set rather than going to higher energy d-orbitals set and as a result low spin complex is
formed.

Case:2 In case of weak field ligand, ∆< 𝑃, thus the electron will go to higher energy d-orbital set
instead of pairing in lower energy sets and as a result high spin complex is formed.

In Configuration of octahedral crystal field.

2. Magnetic Property
We know that low complex are stable in case of strong field ligand and high spin complex are
stable in case of weak field ligand. Thus we can predict whether the complex contain unpaired
electron or not. If the complex contain unpaired electron then it will paramagnetic and if all the
electrons are paired then it will be diamagnetic.
Further magnetic moment of complex can be calculated by following formula.

𝜇 = √𝑛(𝑛 + 2) 𝐵. 𝑀
𝑛 → 𝑛𝑜. 𝑜𝑓 𝑢𝑛𝑝𝑎𝑖𝑟𝑒𝑑 electrons

3. Colour
The colour of coordination compounds is due to electronic transition within d-orbitals.
Explanation
When coordination compound is exposed to light then the electron present in lower energy d-
orbitals set absorb waves of appropriate frequency from visible region and get excited to higher
energy d-orbital set and thus impart complementary colour.
Example:
[𝑇𝑖(𝐻2 𝑂)6 ]3+is purple in colour because the electron present in lower energy 𝑡2 𝑔 set absorb
waves of Blue-green region (𝑣𝜆 = 498𝑛𝑚) from visible region and get excited to higher energy.
Example: Set and thus imparts purple colour.

Explanation:
[𝑇𝑖(𝐻2 𝑂)6 ]3+
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Oxidation state = +3
E.C. in +3 oxidation State= 3𝑑1
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Q. [𝑇𝑖(𝐻2 𝑂)6 ]3+ which is purple in colour becomes colour less on heating explain why?
Because on heating 𝐻2 𝑂 molecules are removed and in absence of ligands there will be no
splitting of d-orbitals and thus electronic transition within d-orbitals in not possible.

Note: The colour of coordination compounds having same central metal ion depends upon
nature of ligand because for different ligand value of 𝐶𝐹𝑆𝐸(Δ) is different and thus the electron
will absorb waves of different wavelength from visible region and will impart different colours.

ℎ𝑐
𝐶𝐹𝑆𝐸(𝛥) = = 𝜆𝑣
𝜆

ILLUSTRATION
Coordination entity wavelength of light absorbed colour of entity
1. [𝐶𝑜𝐶𝑙(𝑁𝐻3 )5 ]2+ 535 violet
[𝐶𝑜(𝑁𝐻 ) (𝐻 3+
2. 3 5 2 𝑂)] 500 Red

Limitations of Crystal Field Theory

1. It consider metal ligand bond to be purely ionic bond and do not take into account the
covalent nature of metal ligand bonding.

2. This theory consider neutral ligands as a point of negative charge. Thus anionic ligands
should exert greatest splitting effect but actually they are found at the lower end of
spectrochemical series.

Metal Carbonyls
The coordination compounds in which carbon monoxide molecules acts as ligands are called
metal carbonyls. They are organometallic compounds.
Example:[𝑁𝑖(𝐶𝑂)4 ], [𝐹𝑒(𝐶𝑂)5 ], [𝐶𝑟(𝐶𝑂)6 ] etc.

Bonding in metal carbonyl

The metal carbon bond in metal carbonyls has both sigma and pi character. The sigma bond is
formed by the donation of electron pair present an carbon atom of ′𝐶𝑂′ molecules into the
empty hybrid orbital of metal atom and pi bond is formed by the donation of lone pair electron
present in filled d-orbital of metal atom into the vacant antibonding molecular orbital of ′𝐶𝑂′
molecules. Such bonding is called Synergic bonding and it’s strengthens (provide strength) to
the metal-carbon bond in metal carbonyls.
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Stability of coordination compound
The stability of complex is expressed in terms of its stability constant. The greater the stability
constant for a complex the more will be its stability.

The Equilibrium constant for the formation of a complex is called its equilibrium formation
constant or stability constant.
Example: Stability for [𝐶𝑢(𝑁𝐻3 )4 ]2+ is expressed as follows:
𝐶𝑢2+ + 4 𝑁𝐻3 ⇌ [𝐶𝑢(𝑁𝐻3 )4 ]2+

[𝐶𝑢(𝑁𝐻3 )4 ]2+
𝐴𝑡 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚 𝛽 =
[𝐶𝑢2+ ][𝑁𝐻3 ]4

The formation of a complex can also be represented in steps.

Example: Formation [𝐶𝑢(𝑁𝐻3 )4 ]2+ is done in following steps:-

Step:1𝐶𝑢2+ + 𝑁𝐻3 ⇌ [𝐶𝑢(𝑁𝐻3 )]2+

[𝐶𝑢(𝑁𝐻3 )]
𝑘1 = … … (𝑖)𝑎𝑡 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛
[𝐶𝑢2+ ][𝑁𝐻3 ]

Step:2[𝐶𝑢(𝑁𝐻3 )]2+ + 𝑁𝐻3 ⇌ [𝐶𝑢(𝑁𝐻3 )2 ]2+

[[𝐶𝑢(𝑁𝐻3 )2 ]2+ ]
𝑘2 = … … . (𝑖𝑖)𝑎𝑡 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛
[[𝐶𝑢(𝑁𝐻3 )]2+ [𝑁𝐻3 ]

Step:3[𝐶𝑢(𝑁𝐻3 )2 ]2+ + 𝑁𝐻3 ⇌ [𝐶𝑢(𝑁𝐻3 )3 ]2+

[𝐶𝑢(𝑁𝐻3 )3 ]2+
𝑘3 = … … (𝑖𝑖𝑖)𝑎𝑡 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛
[[𝐶𝑢(𝑁𝐻3 )2 ]2+ ][𝑁𝐻3 ]

Step:4[𝐶𝑢(𝑁𝐻3 )3 ]2+ + 𝑁𝐻3 ⇌ [𝐶𝑢(𝑁𝐻3 )4 ]2+

[[𝐶𝑢(𝑁𝐻3 )4 ]2+ ]
𝑘4 = … … (𝑖𝑣)𝑎𝑡 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛
[[𝐶𝑢(𝑁𝐻3 )3 ]2+ ][𝑁𝐻3 ]

Here, 𝑘1 , 𝑘2 , 𝑘3 , 𝑘4 ,are step wise stability constant.

Relation between overall stability constant and stepwise stability constant.
𝛽𝑛 = 𝑘1 × 𝑘2 × 𝑘3 … … . . 𝑘𝑛

In Stability Constant (𝒌𝒊 )

The reciprocal of overall stability constant is called instability constant or equilibrium
dissociation constant.
1
𝑘𝑖 =
𝛽𝑛

Factor Affecting Stability of Complex.

1. The greater the charge on central metal ion, the more will be stability of complex.
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2. The smaller the size of central metal ion, the more will be stability of complex.
3. The greater basic nature of ligand, the more will be stability of complex. (𝑒 − donating power)
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4. Presence of chelating ligand increases stability of complex this is known as chelate effect.
Importance and Applications of Complex
1. Analytical Chemistry: EDTA is used in volumetric analysis of 𝐶𝑎2+ , 𝑍𝑛2+ 𝑎𝑛𝑑 𝑀𝑔2+ . Thus
coordination Compounds are used in both qualitative and quantitative analysis of many metals.

2. In metallurgy: Silver and gold are extracted from their ore by treating their ore with aqueous
solution of NaCN. Nickel is extracted from its ore by converting first into a volatile complex
when then dissociates into Ni and CO.
∆
𝑁𝑖 + 4𝐶𝑂 → [𝑁𝑖(𝐶𝑂)4 ]2+ → 𝑁𝑖 + 4𝐶𝑂

3. Electroplating: Metal complexes are also used for electroplating desired objects.

4. Photography

5. In Biological processes

(A) Haemoglobin: It is a kind of protein which carry oxygen in blood for different parts of body.
It is a complex of Fe (ox. state +2). It is red in colour.
(B) Chlorophyll: It plays its important role in photosynthesis. It is a magnesium complex.
(C) Vitamin 𝑩𝟏𝟐 : It is a complex of cobalt. It is red in colour. It mainly found in tissue of animals
and plants.

6. In Pharmaceutical field: 𝐸𝐷𝑇𝐴4− is used for treatment of lead poising. It is also used for water
treatment.
Cisplatin is also used for tumour.

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