CLASS – 12TH

CBSE 2024

COORDINATION
COMPOUNDS
APNI KAKSHA NOTES

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APNI KAKSHA 2
 COORDINATION COMPOUNDS
Addition compounds -: They are formed by the combination of two or more stable
compounds in stoichiometric ratio.

Double salts Coordination Compounds

⇒ Compounds which lose their identity
in solution are called double salts.
K 2 SO4 + Al2 SO4 + 24H2 O
↓
K 2 SO4 ⋅ Al2 (SO4 )3 ⋅ 24H2 O [Alum]
⇒ Compounds which does not lose their
identity in solution are called
coordination compound.
⇒ Fe(CN)2 + 4KCN ⟶ K 4 [Fe(CN)6 ]

2 K + (99: ) + 2Al+3 (9q i ) + 4SO2−

4 (qq ∙) 4 K+ 4−
(aq.) + [Fe(CN)6 ](aq.)

Terminology related to Co-ordination Compounds:-

(a) Co-ordination Entity -: The central atom lion and the ligands attached to it are enclosed
in square brackets are collectively known as co-ordination entity or co-ordination sphere.
Ligand -: The donar atoms, ions or molecules which donate a pair of electrons to the central
metal atom/ion are called ligands.

(b) Denticity:- The no. of donor atoms present in a ligand, is called denticity of ligand.
⇒ Unidentate:- Only one donor atom [Cl− |NH3 |H2 O etc. ]
⇒ Bidentate/ didentate -: When a ligand can bind through two donor atom.
For example ⇒ Ethane-1,2-diamine [NH2 − 1 CH2 − 2 CH2 − NH2 ]
or
Ethylenediamine [en]

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⇒ Polydentate: More than two donor atoms.
For example ⇒ Ethylene diamine tetra-acitate ion
⇒ [EDTA]4−
⇒ It can bind through two nitrogen and four oxygen atoms to a central metal
ion.

(c) Ambidentate Ligand -: Unidentate ligands containing more than one co-ordinating
atoms are ambidentate ligands.

For example ⇒

(d) Co-ordination Number -: The no. of ligand donor atoms to which the metal is directly
bonded.
For example ⇒ [Pt + Cl6 ]2− ∶ C ⋅ N ⋅⇒ 6
[Ni(NH3 )4 ]2+ ∶ C ⋅ N ⋅⇒ 4

(e) Co-ordination Polyhedron -: The spatial arrangement of the ligand atoms which are
directly attached to the central atom/ion defines a coordination polyhedron about the
central atom.

(f) Homoleptic and Heteroleptic Complexes:-

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⇒ Complexes in which a metal is bound to only one kind of donor groups are known as
homoleptic.
For example ⇒ [Co(NH3 )6 ]3+
⇒ Complexes in which a metal is bound to more than one kind of donor groups are known
as heteroleptic complex.
For example ⇒ [Co(NH3 )4 U2 ]+
⇒
Formula IUPAC Name
Pynidine NO Nitrosyl

N̈H3 Ammine NO2 − Nitrio

H2 O Aqua ONO− Nitrito-o
Co Carbonyl NH2− Amido
R − NH2 Alkylamine oxalato [OX]

u− Chloride OH − Hydroxo
Br- Bromide
CN− Cyanido / Cyano
CO3− Carbonato
SCN− Thiocyanato
NCS − isothiocyanato

(g) Oxidation No. of central atom :- oxidation no. of CA + sum of charge on total ligands =
charge on co-ordination Sphere
⇒ [Cu(NH3 )4 ]2+ : oxidation no. of Cu ?
x + 4 (charge on NH3 ) = 2
x + 4 × 0 = 2 then x = +2

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 Nomenclature of Co-ordination Compounds
⇒ Rules for writing formula of mononuclear coordination complexes -:
(a) Formula of Cation [ simple or complex.] is written fir tit.
(b) Co-ordination entity is enclosed in square bracket.
(c) In coordination sphere, metal atom is written first, followed by ligands in alphabetical
order of their names.
(d) In abbreviated ligands [like en, ox] → first letter of abbreviation is Considered.
(e) When ligands are polyatomic, their formulas are enclosed in parenthesis.
For example ⇒ (SCN), (PPh3 ) etc.
(f) There should be no space between the ligands and the metal.
(g) For charged coordination entity -: charge is indicated outside the squat brackets as a
right superscript with the no. before the sign.
For example ⇒ [Co(CN)6 ]3− , [Cr(H2 O)6 ]3+ etc.
(h) The charge of the cation is balanced by the charge of anion.
For example ⇒ [Cr(H2 O)5 Cl]Cl2 ⋅ H2 O
↓ ↓
Alphabetical: Aqua > Chloro
order
Rules for naming of mononuclear coordination compounds –
(a) Complex cation is named first followed by anion (if present).
(b) The ligands are named in alphabetical order before the name of metal atom io
(c) Names of anionic ligands end in - 0.
[for example → cyano / chloride].
Neutral ligands have no special ending
[H2 O → Aqua, NH3 → ammine].
Positive ligands end in -ium.
[ Not: Nitrosonium]
(d) Prefixes mono, di, tr... are used to indicate the number of the individual ligands.
⇒ When the names of ligands include a numerical prefix, then terms, bis, iris, tetrakis are
used, the ligand to which thy refer being placed in paranthesis.
(e) Oxidation state of metal is indicated by Roman numerical in parenthesis.
(f) If complex ion is a cation, the metal is named same as the element.
⇒ If complex ion is an anion, the name of the metal ends with suffix - ate.
⇒ The neutral complex molecule is named similar to that of the complex cation.

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(i) [Cr(NH3 )3 (H2 O)3 ]Cl3 : triamminetriquachromium (III) Chloride
oxidation no. of
Cr + 3( charge on NH3 ) + 3(charge on H2 O) + 3(charge on chlorine) = 0
⇒ oxidation no. of Cr + 3 × 0 + 3 × 0 + 3 × −1 = 0
⇒ oxidation no. of cr = +3
(ii) [Co(NH2 − CH2 − CH2 − NH2 )3 ]2 (SO4 )3 : tris (ethane-1,2-diamine) Cobalt (II) sulphur
⇒ 2(x + 3 × 0) + 3(−2) = 0
⇒ x = +3
(iii) [Ag(NH3 )2 ] [Ag(CN)2 ] : diammine silver (I) dicyanoargentate (I)
↓ ↓
⨁ ve complex ion ⊝ ve complex ion
(iv) Ni(CO)4 : Tetracarbonylnickel (O)
⇒ x + 4(0) = 0
then x = 0
chloro / chlorido → Cl.
(v) K 4 [Fe(CN)6 ]
Potassium hexacyanido ferrate (II).
4(+1) + x + 6(−1) = 0
then x = +2
(vi) [Pt(en)2 C2 ]2+ : dichlorobis (ethane-1,2-diamine) platinum (IV) ion
(vii) [Ni(NH3 )6 ]U2 : hexaaminenickel (II) chloride
(viii) [P + U(NH2 CH3 )(NH3 )2]Cl : diammine chloride methylamine platinum (II) chloride
(ix) [Pt(NH3 )4 Cl2 ]U2 : tetraaminedichlorido platinum (IV) chloride
(x) [Cr(NH3 )6 ] [Co(CN)6 ] : hexaammine chromium (II) hexacyanocobaltate (III)
↑ ↑
⨁ ve complex ion ⊝ ve complex ion
# [Pt(NH3 )3 (NO)Cl2 ]Br2 : thiamine dichloridonitrosyl platinum (IV) bromide
# [Co(CN)2 (NH3 )4 ]Cl : tetraammine dicyano cobalt (III) chloride
# [Cr(NH3 )5 (NCS)] [ZnCl4 ] : pentaammine isothioeyanato chromium (III) tetrachlorido
↑ ↑ zincate (II)
⨁ ve complex ion ⊝ ve complex ion
# [Cr(NH3 )2 Cl2 (en)]Cl : diamminedichlorido (ethane-1,2-diamine) chromium (II) chloride
# k 3 [FeCN (N)6 ] : Potassiumhexacyanoferrate (III)

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# [Co(NH3 )6 ]Cl3 : hexaammine cobalt (III) chloride
# [Co(en)3 ]3+ : this (ethane-1,2-diamine) cobalt (III) ion.
# [NiCl4 ]2− : Tetrachloridonickelate (II) ion.
# [Co(NH3 )5 (NO2 )]2+ : Pentaammine nitrite −N cobalt (III) ion.
# [Pt (NH3 )2 U2 ] : Diammine dichlorido platinum (II).
⇒ Co-ordination No → Q
⇒ oxidation state ⟶ +2
3−
COO−
# [co ( | ) ] : Trioxalato cobaltate (III) ion.
−
COO 3
# [Cr(Co)6 ] : Hexacarbonylchromium (0).
# [Pt Cl3 (C2 H4 )] : Trichlorido ethene platinum (IV)
# [Co Br2 (en)2 ]+ : Dibromidobis (ethare -1,2-diamine) Cobalt (III) ion.
# K 3 [Fe(C2 O4 )3 ] : Potassiumtrioxalato forrate (III) ion.
# [Pt (NH3 )6 ]U4 : Hexaamine platinum (IV) chloride
# [Cr(C2 O4 )3 ]3− : Trioxalato chromate (III) ion
# [Co(en)2 U2 ]+ : Dichloridobis (ethane-1,2-diamine) Cobalt (III) ion
⇒ Hexaammine cobalt (III) sulphate : [Co(NH3 )6 ]2 (SO4 )3
Potassiumtrioxalato chromate (III) : K 3 [Cr(C2 O4 )3 ]
Potassiumtrioxalato aluminate (III) : K 3 [Al(C2 O4 )3 ]
Dichloride bis (ethane-1,2-diamine) cobalt (III) ion : [CoCl2 (en)2 ]+
⇒ Pentaamminenitrito-0-cobalt (III) ion : [Co(NH3 )5 (ONO)]2+
⇒ Sodiumdicyanidoaurate(I) : Na[Au(CN)2 ]
⇒ Tetraammine chloridonitrito −𝐍 - platinum (IV) sulphate : [Pt(NH3 )4 U(NO2 )]SO4
⇒ Mercury tetrathiocyanatocobaltate (III) : Hg[Co(SCN)4 ]
⇒ Potassium trioxalato aluminate (III) : K 3 [Al(C2 O4 )3 ]
⇒ Potassium tetrahydroxozincate (II) : K 2 [Zn(OH)4 ]

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Werner's Theory:- Werner was the first to formulate his idea about the structures of
coordination compounds. The main postulates are
(i) In coordination compounds metals show two types of valency → Primary and secondary
(ii) The primary valences are normally ionisable and are satisfied by negative ions.
(iii) The secondary valences are non-ionisable. These are satisfied by neutral molecules or
negative ions.
(iv) The ions/groups bound by secondary valency to metal have spatial arrangements
Corresponding to different coordination numbers.
NOTE:- In modern formulation -: Primary valency corresponds to oxidation State of metal.
⇒ Secondary valency corresponds to coordination No. of central metal.
⇒ Spatial arrangements are called coordination polyhedra.
Experiments -:
(1) In a series of compounds of cobalt (III) chloride with ammonia, it was found that some of
chloride ions could be precipitated as Age on adding exes AgNO3 solution but some
remained in solution.
AgNO3
⇒ CoCl3 . 6NH3 
excess
 3 mol AgCl
AgNO3
[Co(NH3 )6 ]Cl3 
excess
 3 Ag Cl + [Co(NH3 )6 ]3+

↓ ↓
Secondary Primary
valency valency

CoCl3  5NH3 AgNO

 3
excess
 2 mol AgCl

Co  NH3 5 Cl  Cl2 AgNO

 5NH3 &
 3
 2 AgCl  Co  NH3 4 Cl2   AgCl 3Cl−
excess
2Cl−
⇒ CoCl3  5NH3 AgNO
 3
excess
 1 mol AgCl
 4NH3 &
Co  NH3 4 Cl2  Cl 
AgNO3
  Co  NH3 4 Cl2   AgCl 3Cl−
excess
2Cl−
↓ ↓
Coordination Co in (III)
No. = 6 oxidationstate

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(2) As we know conductivity of a solution depends on no. of ions present in solution.

⇒ When a coordination compound CrCl3 ⋅ 6H2 O is mixed with AgNO3 , 2 moles of AgCl2 are
precipitated per mole of compound.
AgNO3
(i) Write structural formula -: CrCl3 ⋅ 6H2 O ⟶ 2 AgCl ↓ : means that 2C− is ionisable.
⇓
[Cr(H2 O)5 U]U2 ⋅ H2 O
(ii) IUPAC Name of complex:- Pentaquin chloride chromium (II) chloride

Valence Band Theory

⇒ According to this theory, the metal ion or atom under the influence of ligand can use its
(h − 1)d, hs, np/ns, np, nd orbitals for hybridisation to give a set of equivalent orbitals of
definite geometry.
⇒ These hybridised orbitals are allowed to overlap with ligand orbitals that can donate
electron pairs for bonding.

⇒ It is possible to predict the geometry of a complex from the knowledge of its magnetic
behaviour on the basis of NBT.
⇒ Magnetic moment of a complex depends on no. of Unpaired electrons.

Magnetic moment μ = √n(n + 2) n = No. of unpaired electron.

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Example -:
(i) [Co(NH3 )6 ]3+ : Diamagnetic in nature

⇒ Inner Orbital complex: d2 sp3 : Low spin complex: spin paired complex.
⇒ outer orbital complex: sp3 d2 : High spin complex: spin free complex.
(ii) [Cof6 ]3− : Paramagnetic Octahedral complex.
(Presence of unpaired electrons.)

(iii) [NiCl4 ]2− : Paramagnetic in nature.

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(iv) Ni(CO)4 : Diamagnetic in nature.

(v) [Ni(CN)4 ]2− : Square Planar Complex: Diamagnetic.

⇒ [Mn(CN)6 ]3− : Magnetic moment of 2 electrons: d2 sp3 : Paramagnetic

[MnCl6 ]3− : Magnetic moment of 4 electrons: sp3 d2
⇒ [Fe(CN)6 ]3− : m = √n(n + 2 = √1(1 + 2) : 1 unpaired electron: d2 sp3

[fe f6 ]3− : μ = √5(5 + 2): 5 unpaired electrons: High spin complex [sp3 d2 ]
⇒ [Co(C2 O4 )3 ]3− : Diamagnetic: d2 sp3 : Inner orbital complex.
[Cof6 ]3− : Paramagnetic with four unpaired electron: sp3 d2
Limitation of VBT -:
(i) It involves no. of assumptions.
(ii) It does not explain colour of coordination compounds.
(iii) It does not give explanation of kinetic and thermodynamic stabilities of complex.
(iv) It does not distinguish between week and strong ligands.

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 Crystal field Theory
⇒ CFT is an electrostatic model which considers the metal-ligand bond to be ionic, arising
purely from electrostatic interactions between the metalion and ligand.
⇒ Ligands are treated as point charges in case of anions or dipoles in case of neutral
molecules. (H2 O/NH3 etc.) ↓
[Cl− , Br − , OH − etc.]
Crystal Field splitting in Octahedral complexes:-
⇒ Under the influence of 6 ligands field, degeneracy of d orbitals has been removed due to
ligand-metal electron repulsions in octahedral complex.
⇒ Removal of degeneracy give three orbitals [dxy , dyz , dzx ] of lower ewergy (t 2g ) and two
orbitals of higher energy [dz2 , dx2 −y2 = eg set ].
⇒ dx 2 − y 2 and dz 2 orbitals point towards the axes along the direction of the ligand, will
experience. more repulsion and will raised in evergy.
⇒ dxy , dyz , dzx orbitals are directed between axes, will be lowered in ehergy relative to
average ehergy (in the sfherical cystal field).
⇒ Splitting of degenerate levels due to the presence of ligands in a definite geometry. is
called crystal field splitting and the ehergy seperation is denoted by Δ0 [ crystal field
splitting energy].

⇒ The extent of splitting depends upon the field produced by ligand and charge on metal
ion.

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Spectrochemical series:-
⇒ If ligands are arranged in a series in the order of increasing field strength, then that series
is called spectrochemical series.
⇒ halogen donors < oxybenzones: < Nitrogen dinars < Carbon donors:

(i) If Δ0 > p
Now 4th electron enters into t 2g orbital and configuration = t 42g e0g
⇒ Ligands for which Δ0 > P are known as strong field ligand. [SFL]
(ii) If Δ0 < P, are known as
Here, 4th electron enters one of eg orbitals giving the configuration t 32g e1g .
⇒ Ligands for which Δ0 < P, are known as weak field ligand. [WFL]
⇒ I − < Br − < SCN − < Cl− < S 2− < F − < OH − < C2 O2− −
4 < H2 O < NCS < EDTA
4−

< NH3 < en < CN − < CO

⇒ Generally, CN− & CO are SFL with M +2 and rest ligands are WFL.
⇒ CN, Co, en, NH3 & H2 O are SAL with M +3.

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Question:- (i) [Cof6 ]3− (ii) [Co(en)3 ]3+ (iii) [Co(NH3 )6 ]3+
⇒ f − as WAL. ⇒ en as SAL ⇒ NH3 as SFL.
Crystal field splitting in tetrahedral complexes:-
⇒ In tetrahedral coordination entity formation the orbital splitting is inverted and is smaller
as compared to the octahedral field splitting.
4
⇒ For same metal and ligand: Δt = 9 Δ0

[ML6 ] → Δ0
[ML4 ] → Δt

Colour in Coordination Compounds

⇒ When light of certain frequency falls on the complex, it absorbs light from visible range
for transition of electrons from lower d -energy level to higher d energy level. This
transition is called d-d transition of electron.
⇒ Colour of the compound is the complementary colour of absorbed light. For example if
green is absorbed by the complex, it appears red.
⇒ [Ti(H2 O)6 ]3+ : Voilet in colour.
⇓
d1 −: t12g eg 0
Transition: t12g eg 0 to t 02g eg1

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⇒ In absence of ligand crystal field splitting does not occur and hence the substance is
colourless.

Relationship between the Wavelength of Light absorbed and the Colour observed in some
Coordination Entities

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Limitations of CFT:- From the assumptions that the ligands are point charges it follows
that anionic ligands should exert the greatest splitting effect. But its
not true because anionic ligands are found at the low end of
spectrochemical series.
Bonding in metal carbonyls

⇒ Compounds which have at least one metal -carbon bond are called Organometallic
Compounds.
⇒ The metal carbon bond in metal carbonyls possesses both σ and π character.
⇒ The M − Cσ bond is formed by the donation of lone pair of electrons on the carbonyl
carbon into a vacant orbital of metal.
⇒ The M − C K bond is formed by the donation of a pair of electron from a filled d-orbital of
metal into vacant π∗ orbital of CO.
⇒ The metal to ligand bonding creates a Synergic Effect which strengthens the bond

between CO and the metal.

Stability of coordination compounds

⇒ The stability of complex in solution refers to the degree of association between the two
species involved in the state of equilibrium.
⇒ Equilibrium constant for the association expresses the stability.
M + 4L ⇌ ML4 Value of equilibrium constant ↑ ⇒ [ML4 ] ↑

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⇒ Stepwise stability constant : The equilibrium constant of each step of a complex
reaction is called stepwise stability constant (k1 , k 2 ⋯ )
⇒ Overall stability constant : The equilibrium constant for net reaction.
(β4 )
⇒ (i) M + L ⇌ ML k1 = [ML] ∣ [M][L]
(ii) ML + L ⇌ ML2 k 2 = [ML2 ] ∣ [ML][L]
(iii) ML2 + L ⇌ ML3 k 3 = [ML3 ] ∣ [ML2 ][L]
(iv) ML3 + L ⃗<
⃗ ML4 K 4 = [ML4 ] ∣ [ML3 ][L]
M + 4L ⇌ ML4 β4 = [ML4 ] ∣ [M][L]4

Then → β4 = k1 ⋅ k 2 ⋅ k 3 ⋅ k 4

APNI KAKSHA 18
 Important Previous Year Questions.
(i) What is meant by chelate effect?
⇒ When a didentate | polydintate ligand containing donor atoms positioned in such a way
that, they coordinate with the central metal ion forming a five or six membered ring. The
effect is called chelate effect.
⇒ As a result of chelate effect, the stability of the complex increases.

(iii) CO is stronger comflexing agent than NH3 , Why?

⇒ There exist a back bonding in c0 complexes in which c0 accepts electron density from the
filled d orbitals of metal atom into their π∗ orbital. So, there are σ as well as T interaction
with metal in case of CO . But NH3 makes only σ bard with metal. Therefore co is a
stronger complexing agent than NH3 .
(iv) Write the state of hybridisation, the shape and the magnetic behaviour of following
complex entities.

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# 𝐊 𝟒 [𝐌𝐧 (𝐂𝐍)𝟔 ]: IUPAC Name: Potassium hixacyano magahate (II)
4(+1) + x + 6(−1) = 0
Thin x = +2

Isomerism in Coordination Compounds

⇒ Isomerism arises due to different structural arrangements [Structural Isomer] or special
arrangements [stereoisomerism] of compounds having same formula.
Structural Isomerism -:
(i) Ionisation Isomerism-: When the complexes with same composition give different ions
in solution.
Example: [Co(NH3 )5 Br3 ]SO4 and [Co0 (NH3 )5 SO4 ]Br
↓ ↓
[Co(NH3 )5 Br]2+ + SO2−
4 [Co(NH3 )5 SO4 ]+ + Br −
(ii) Solvate I Hydrate Isomerism-: When complex differ in the number of water (solvent)
molecules present as ligand.
Example-: [Cr(H2 O)6 ]Cl3 and [Cr(H2 O)5 Cl]Cl2 ⋅ H2 O and [Cr(H2 O)4 O2 ]C ⋅ 2H2 O

APNI KAKSHA 20
(iii) Linkage Isomerism-: When complexes differ only in the point of attachment of the
ambidentate ligand with central metal atom.
Example-: [CO(NH3 )5 (NO2 )]U2 and [Co(NH3 )5 (ONO)]Cl2
[CO(NH3 )5 (NCS)]Cl2 and [CO(NH3 )5 (SCN)]Cl2
(iv) Coordination Isomerism-: When the interchange of the ligands take place between ionic
and anionic entities of different metal ions present in a complex.
Example-: [CO0 (en)3 ][Cr(NN)6 ] and [Cr(eh)3 ][Co(CN)6 ]
⇒ [Pt(NH3 )4 ][C4 C4 ] and [Cu(NH3 )4 ][PtCl4 ]
Stereo-isomerism:-
(a) Geometrical Isomerism:- When similar groups are present in adjacent position, it is cis.
When they are present in opposite position, it is trans.
⇒ It occurs in square planar compounds and octahedral compounds.
⇒ Geometrical Isomers of [Pt(NH3 )2 C2 ]

⇒ Geometrical Isomers of [Co(NH3 )4 (Cl2 ]+

⇒ Geometrical Isomers of [CoCl2 (eh)2 ]:

⇒ Geometrical Isomers of [Ma3 b3 ]

→ Facial [fac]
→ Meridional [mer]

APNI KAKSHA 21
Example -: [Co(NH3 )3 (NO2 )3 ]
(B) Optical Isomerism -: This is shown by complexes whose mirror images are non-
superimposable. Such complexes are called optical isomers.
⇒ Optical isomers (d and l) of [Co0 (en)3 ]3+ :

⇒ Optical isomers (d and l) of cis [PtU2 (en)2 ]2+ :

⇒ trans [Pt Cl2 (en)2 ]2+ is optically inactive.

APNI KAKSHA 22
Example: Draw structures of geometrical isomers of [Fe(NH3 )2 (CN4 ]−
Solution:

Example: Out of the following two coordination entities which is chiral (optically active)?
(a) cis − [CrCl2 (ox)2 ]3− (b) trans- [CrCl2 (ox)2 ]3−
Solution: The two entities are represented as

(a) cis - [CrCl2 (ox)2 ]3− (b) trans - [CrCl2 (ox)2 ]3−
Out of the two, (a) cis - [CrCl2 (ox)2 ]3− is chiral (optically active).

APNI KAKSHA 23