Coordination Compound

Co-ordination Compound

Ligand:- Those neutral or ionic species which attach with central metal ion by
co-ordinate bond are called as Ligand.
 The atom which form co-ordinate bond is known as donor atom.
 The number of atom decides the type of ligand.
Types of Ligands:-
Ligands are of 6 types:
Monodentate, Bi, Tri, Tetra, Penta and Hexadentate ligands.

1. Monodentate Ligands: Those ligands which form 1 co-ordinate bond by

donating 1 pair of electrons to CMI are called Monodentate Ligands.
Monodentate Ligands are of three types: Negative, Positive and Neutral
Ligands
(i) NEGATIVE LIGANDS – Suffix of negative ligand is ‘O’
S.No Formula Name as Ligand
- - - -
1 X (Cl , Br , I ) Halido(Chlorido, Bromido, Iodido)
-
2 OH Hydroxo
-
3 CN Cyano or Cynaido
-2
4 O Oxo
-2
5 O2 Peroxo
-
6 NH2 Amido
-2
7 S Sulphido
-3
8 N Nitrido
-3
9 P Phosphido
-
10 CH3COO Acetato
-
11 NO3 Nitrato
-
12 NO2 Nitro
-
13 ONO Nitrito
-2
14 CO3 Carbonato
-2
15 SO4 Sulphato
-2
16 SO3 Sulphito
-
17 CNS Thiocyanato
-2
18 S2O3 Thiosulphato

(ii) POSITIVE LIGANDS – Suffix of positive ligand is ‘ium’

S.No. Formula Name of Ligand
01 NO+ Nitrosoium
+
02 NO2 Nitronium
+
03 NH4 Ammonium
04 Cl+ Chloronium
+
05 NH2–NH3 Hydraznium

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 Coordination Compound

(iii) NEUTRAL LIGANDS – There is no Suffix.

S.No. Formula Name of Ligand

1 H2O Aqua(Aquo)
2 NH3 Ammine
3 CO Carbonyl
4 CS Thio Carbonyl
5 NO Nitrosyl
6 NS Thionitrosyl
7 C6H5N Pyridine

2. BIDENTATE LIGANDS

S.No. Formula Name of Ligand

01 O=C-O- Oxalato(OX)
O=C-O-
02 Me-C=NO- Dimethyl glyoximato (DMG)
Me-C=NOH
03 H2N-CH2-COO- Glycenato(gly.)
04 2, 2’-bipyridyl(bipy)
05 (CH3)2C – CH2 Isobuteylene diamine
NH2 NH2 (I-bn)
06 H2N – CH2 – CH2 – NH2 Ethylene Diamine (en)

3. TRIDENTATE LIGANDS
(i) Diethylene triammine (dien) H2N– CH2 – CH2 – NH – CH2 – CH2 – NH2

(ii) 2, 2’, 2’’ – terphyridine (terpy)

4. TETRA – DENTATE LIGANDS

(i) Triethylene tetrammine (trien)

H2N– CH2 – CH2 – NH – CH2 – CH2 – NH – CH2 – CH2 – NH2

(ii) Nitrilotriacetate (N.T.A) CH2COO-

N CH2COO-
CH2COO-
5. PENTADENTATE LIGANDS

Ethylene diamminetriacetate ion

-
OOCH2C CH2COO-
N - CH2 – CH2 - N
-
OOCH2C H

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 Coordination Compound

6. HEXADENTATE LIGAND

Ethylene diammine tetracetate ion (E.D.T.A.)

-
OOCH2C CH2COO-
N - CH2 – CH2 - N
-
OOCH2C CH2COO-

Chelate Ligand or Compound :- When polydentate ligands attached with central metal ion, it form
a ring structure. These compounds are called as chelate compounds and ligands are called as chelate
ligands.

Note: Chelate compounds are more stable than the normal complex compounds; due to ring formation
takes places in chelate compounds.

Ambident Ligands:- Those monodentate ligand in which two donor atoms are present are called as
Ambident Ligands.

For eg.: CN cyno & N ≡ C Isocyno

NO2 (Nitro) & -O - N = O (Nitrito)

IUPAC of monocentral complex compounds:

[Cr (NH3)6]Cl3

Coordination sphere Central Metal Ion Ligand Coordination no. Ionic Sphere

There are 6 rules:

1. The order of +ve & -ve part → We write the 1st IUPAC name of +ve part
and than –ve part.
Case 1: Normal +ve ion & complex –ve ion.
Eg: K4 [Fe (CN)6]
Case 2: Complex +ve ion & normal –ve ion
Eg: [Cr (NH3)6] Cl3 etc.
Case 3: +ve & -ve both ions are complex
Eg: [Cu (NH3)4] [CuCl4]

2. Order of Ligands → According to the new rule from (1971) all ligands are
written in alphabetical order
Eg: CN-, H2O, Cl-, NO2-
Order = aqua → chlorido → cyano → nitro
3. Suffix of the ligands → 3 parts
(a) For –ve ligand: → The word ‘O’ is attached as suffix in the name of the –ve ligands.
For eg CN- Cyano
Cl- Chlorido
-
NH2 Amido

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 Coordination Compound
(b) For +ve ligand: → The word ‘ium’ is attached as suffix in the name of the +ve
Ligands. For eg NO+ Nitrosoium
Cl+ Cloronium
(c) For neutral ligand: → only simple name are written in the IUPAC.
Eg H2O = aqua ; CO = Carbonyle; CS = Thiocarbonyle.

4. Numerical prefix of the ligand:- If any ligands are present more than one
time in complex compound then following words are used before
the name of the ligands.
Case 1: For monodentate ligands – If any ligand present for 2, 3, 4………6 times then di,
tri, tetra…….hexa words respectively are attached before the name of the ligand.
Eg. (Cl)4 Tetra Chlorido
(H2O)6 Hexa Aqua
Case 2: For polydentate ligands –
(a) If di, tri, tetra…. Words are present in the original name of ligand even then they
are present 2, 3, 4….. times then bis, tris, tetrakis etc words are attached before the
name of ligand & ligand name written in brackets.
Eg. (en)3 Tris(Ethylenediamine)

(b) If di, tri, tetra…. Etc Words are not present in the original name of polydentate
ligand even then they are present 2, 3, 4….. times then di, tri, tetra…etc words are
attached before the name of ligand
Eg. (OX)3 Trioxalato

5. Write the Oxidation state of central metal ion.(CMI)

Determine the oxidation state of CMI with the help of Oxidation number method and write its
oxidation state in roman number in small brackets after the name of CMI.

6. Suffix of metal ion (or CMI) : Three parts

(a) For –ve complex ion : The word “ate” is added as a suffix in the name of
CMI.
(b) For +ve complex ion: Simple name of CMI is written
(c) For neutral complex simple name of CMI is written

Note: In some metal “ate” word is added in general names of the metal ion while in some metal
the “ate” word is attached in ‘latin’ word of the metal.

Table 1:

S.No Metal IUPAC Part

1 Nickel(Ni) Nickelate
2 Chromium(Cr) Cromate
3 Cobalt(Co) Cobaltate
4 Molibednum(Mo) Molibedate

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 Coordination Compound
Table 2
S.No. Metal IUPAC part
1 Silver(Ag) Argentate
2 Gold(Au) Aurate
3 Iron(Fe) Ferrate
4 Copper(Cu) Cuprate
5 Tungsten(w) Walformate
6 Lead(Pb) Plumbate
Ex. 1 Fe4 [Fe (CN)6]3 Iron(III) hexacyanoferrate(II)

Ex. 2 [Cr (NH3)2(H2O)2(NO2)2]Cl Diaminediaquodinitrochromium(III) chloride

Ex. 3 [Pt (NH3)4] [CuCl4] Tetramineplatinium (II) tetrachloridocuprate (II)

IUPAC of polycentral complex compounds:-

1. When two central metal ion are present in complex compound.

2. Bridge ligands: - Those ligands which are attached with two CMI are known as bridge ligands.
For Bridge ligand “µ” (mu) indication is written before the name of bridge ligand with hyfen(-)
and remaining are old rule.
OH
e.g., [(NH3)4 Fe Fe (H2O)4] Cl4
NH2
Tetramineiron(III)-µ-amido-µ-hydroxotetraaquoiron(III)chloride.

Isomerism in complex compounds: - they are of two types.

1. Structural isomerism 2. Sterio isomerism
(i) Ionization iso (i) Geometrical
(ii) Hydrate iso (ii) Optical
(iii) Co–ordinate iso
(iv) Linkage iso
(v) Polymeric iso

1. Ionization isomerism: - Those compounds which have same molecular formula but
have different ion in the solution.
e.g. [Cr (NH3)5 Cl] Br and [Cr (NH3)5Br] Cl
e.g. [Co (NH3)4OH NO2] Br and [Co (NH3)4 Br OH] NO2

2. Hydrate Isomerism: -Those compound which have same molecular formula but different no. of
water molecules in co–ordination sphere known as hydrate isomer and this phenomenon is
known as Hydrate isomerism.
e.g., (a) [Cr (H2O)6] Cl3 and (b) [Cr (H2O)5Cl] Cl2 . H2O
e.g., (c) [Cr (H2O)4 Cl2]Cl . 2H2O and (d) [Cr (H2O)3 Cl3] 3H2O

Note : - With the help of AgNO3 Soln compound ‘a’ can give the 100% ppt of chloride ion. (b)
gives 66% ppt of chloride ion. (c) Gives 33% ppt of chloride. While (d) can not give ppt of
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 Coordination Compound
chloride ion. i.e., those ions which are present in C.S. can not give test by any method while ions
which are present I.S. can be tested by any suitable test.

3. Co–ordination isomerism: - Those compounds which have same molecular formula but their
ligands are exchanged known as co–ordination isomer.
e.g., [Pt (NH3)4] [CuCl4] and [Pt (NH3)3Cl] [Cu (NH3) Cl3]
e.g., [Pt (NH3)4] [CuCl4] and [Cu (NH3)4] [Pt Cl4]

4. Linkage isomerism: - Those compounds which have same molecular formula but the metal
attached with ambident ligand known as linkage isomer.
e.g., [Cr NO2 (H2O)5] Cl2 and [ Cr ONO(H2O)5] Cl2

5. Polymer isomerism: - Those compounds which have same empirical formula but different
molecular weight are known as polymer isomer and phenomenon is known as polymer
isomerism.
e.g., [ Pt (NH3)2Cl2] and [ Pt (NH3)4] [PtCl4]

Sterio isomerism: - Those compounds which have same molecular formula and same structural
formula but different arrangement of the species in space are known as sterio isomer and
phenomenon is known as sterio-isomerism.

1. Geometrical isomerism: - It is due to ligand occupying different position around CMI.

(i) Cis-form (i.e., same gp present in same side)
(ii) Trans-form (i.e., same gp present in opposite side)
Note : - Except the trans-form remaining forms are known as cis-form.
a. Geometrical isomerism in complexes of Co.No. 4 : - These compounds have sp3 and dsp2
i.e., tetrahedral and square planner geometry respectively but the G iso is not possible in
tetrahedral geometry. This is due to all the position are adjacent to one another in these
complexes.
However square planer complexes show geometrical isom

Ma4 Ma3b Ma2b2 Ma2bc M(ab)2 Mabcd

Where – M = CMI & a, b, c, d are monodentat ligand

(ab) = unsymmetrical bidentate ligand

Case.1.- Ma2b2 type eg [ Pt(NH3)2 Cl2]

a a b a

M M

b b a b
Cis-form trans-form

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 Coordination Compound
Case. 2.- Ma2bc type Ex. [ Pt (NH3)2Cl Br]

NH3 NH3 NH3 Cl

Pt Pt

Cl Br Br NH3
Cis-form trans-form

Case.3.- M(ab)2 type Eg. [Pt (gly)2]

CH2 NH2 NH2 CH2 CH2 NH2 O CO

Pt Pt
CO O O CO CO O NH2 CH2

Cis-form trans-form

Case.4.- Mabcd type Eg. [ Pt (NH3) (HO) Cl Br]

a b a c a d

M M M

d c b d c b

Compounds of Co.No. = 6 :- i.e. Octahedral compounds hybridization = sp3d2

Ma6 Ma5b Ma4b2 Ma3b3 Ma2b2c2 M(aa)2b2 M(aa)2bc Mabcdef

Cl Cl

H3N Cl H3N NH3

Co Co

H3N NH3 H3N NH3

NH3 Cl
( Cis-form ) (Trans-form)

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 Coordination Compound
b. Octahedral complexes of the type Ma3 b3 e.g., [ Co (NO2)3 (NH3)3] also exist into
geometrical isomers. (i.e., facial and meridional iso) in facial or Fac isomer the three
ligands are at the corners of a triangular face while in meridional isomers the three ligands
are at the three corners of a square plane as shown below.

NO2 NH3

H3N NO2 O2N NO2

Co Co

H3N NO2 H3N NO2

NH3 NH3

Facial-Isomer Meridional-Isomer

2. Optical isomerism: -The isomers which rotate the plane polarized light equally but in opposite
direction are called optically active isomers.
Optical isomerism shows by octahedral complex compounds i.e., Co.No. = 6. out of
which only “ cis-form represent optical isomerism”. Optical isomers may be dextro–form
or leavo–form
 Dextro or D – form: - Rotate plane polarized light in clock wise direction.
 Leavo or L – form: - Rotate plane polarized light in anti – clock wise direction.
Optical isomerism shown by following types

Ma6 Ma5b M(aa)3 M(ab)3 Ma2b2c2 M(aa)2b2 M(aa)2bc Mabcdef

Ex. M(aa)3 – type. eg [ Co (en)3]+3 only cis - form

en en

en Co Co en

en en

( d - form ) ( l - form)

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 Coordination Compound
Eg. M(aa)2b2 – type eg cis [ Co Cl2 (en)2]
Cl Cl

Cl Cl

en Co Co en

en en
(d - form ) (l – form)

Valence Bond theory for bonding in co – ordination compounds: - Assumptions: -

(i) The CMI provides empty orbitals for the formation of co–ordination bond with suitable ligands.
The no. of ligands is equal to co–ordination no. of CMI.

(ii) The appropriate atomic orbitals (s , p and d) of the metal hybridize to give a set of equivalent
orbitals of definite geometry such as square planner, tetrahedral, octahedral and so on.
sp3 = tetrahedral dsp2 = square planner
3 2 2 3
sp d or d sp = octahedral
(iii) The d – orbital involved in the hybridization may be either inner d – orbitals i.e., (n – 1) d or outer
d – orbitals i.e., nd.
(iv) Each ligand has at least one orbital containing a lone pair of electrons.

(v) The empty hybrid orbitals of metal ion overlap with the filled orbitals of the ligands to form metal
ligand co–ordinate covalent bonds.

Hybridization in complex compounds: -

(i) Low spin or inner orbital complex or hyperligated complex: - When (n – 1) d orbitals
are used in hybridization. E.g., dsp2 , d2sp3
Maximum two d – orbitals are used in hybridization i.e., dz2 & dx2-y2.

(ii) High spin complex or outer orbital complex or hypoligated complex: - When ‘nd’
orbitals are used in hybridization.
e.g., sp3d, sp3d2& sp3d3
(iii) Strong field ligand: - CO > CN- > NO2- >bipy > en > NH3 etc.

(iv) Weak field ligand: - py > SCN > H2O > C2O4-2 > OH- > X- etc.

Note: - Strong ligands normally show d – d transition i.e., rearrangement of electrons

from d – orbital to other orbital in the same orbit. Weak ligands not show d – d transition
or rarely show d – d transition.

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 Coordination Compound
(v) Magnetic characters: -
(a) paramagnetic : - When unpaired electrons are present in d – orbital
(b) Diamagnetic : - When unpaired e-s are not present ( or all e-s are paired )

In Hybridization 3 rules are used: -

a. Determine the oxidation state of CMI.
b. Write the electronic configuration of CMI in above O. S
c. On the bases of number and nature of ligands and magnetic character and hybridization of
complex ion determine.
Note : - (i) Carbonyl ligand (i.e. CO) always attached with CMI in zero oxidation state.
e.g., [Ni (CO)4]º [ Fe (CO)5]º [Cr (CO) 6] etc.

E.g.1. [Ni (CN)4]-2

Oxidation state of Ni = +2
Electronic configuration of Ni+2 = 1s2 …… 3d8 4sº
3d8 4s0 4p0
↑↓ ↑↓ ↑↓ ↑ ↑

Due to presence of strong ligands

d-d transition takes place i.e., pairing
against Hunds rule takes place.
↑↓ ↑↓ ↑↓ ↑↓

Hybridization = dsp2 CN CN CN CN
Magnetic nature = Diamagnetic
Inner orbital complex or low spin complex
shape = square planer

E.g., 2. [NiCl4]-2
Oxidation state of Ni = +2
Electronic configuration of Ni+2 = 1s2 ………… 3d8 4sº
3d8 4s0 4p0
↑↓ ↑↓ ↑↓ ↑ ↑

Due to presence of weak ligands no

d-d transition. And hence no pairing
against Hunds rule.
↑↓ ↑↓ ↑↓ ↑ ↑

Cl Cl Cl Cl
3
Hybridization = sp
Shape = tetrahedral
Magnetic nature = paramagnetic; High spin complex.

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 Coordination Compound

E.g.,3. [Ni (CO)4]º

Oxidation state of Ni = 0
Electronic configuration of Ni0 = 1s2 ………… 3d8 4s2
3d8 4s2 4p0
↑↓ ↑↓ ↑↓ ↑ ↑ ↑↓

Due to presence of strong ligands

d-d transition takes place i.e., pairing
against Hunds rule takes place.
↑↓ ↑↓ ↑↓ ↑↓ ↑↓

CO CO CO CO
Hybridization = sp3
Magnetic nature = diamagnetic
Shape or geometry = tetrahedral
High spin complex complex.

Eg. 4. . [Pt (NH3)4]+2

Oxidation state of Pt = +2
Electronic configuration of Pt +2 = 1s2 …… 5d8 6sº
5d8 6s0 6p0
↑↓ ↑↓ ↑↓ ↑ ↑

Due to presence of strong ligands

d-d transition takes place i.e., pairing
against Hunds rule takes place.
↑↓ ↑↓ ↑↓ ↑↓

NH3 NH3 NH3 NH3

2
Hybridization = dsp
Magnetic nature = Diamagnetic
Inner orbital complex or low spin complex
Shape = square planer

Eg.5. [Fe (CN)6]-4

Oxidation state of Fe = +2
Electronic configuration of Fe+2 = 1s2 …… 3d6 4sº

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 Coordination Compound
3d6 4s0 4p0
↑↓ ↑ ↑ ↑ ↑

Due to presence of strong ligands

d-d transition takes place i.e., pairing
against Hunds rule takes place.
↑↓ ↑↓ ↑↓

CN CN CN CN CN CN
2 3
Hybridization = d sp
Magnetic nature = Diamagnetic
Inner orbital complex or low spin complex
shape = Octahedral

Eg.6. [Fe Cl6]-3

Oxidation state of Fe = +3
Electronic configuration of Fe+3 = 1s2 …… 3d5 4sº
3d5 4s0 4p0
↑ ↑ ↑ ↑ ↑

Due to presence of weak ligands no

d-d transition i.e., no pairing
against Hunds .

↑ ↑ ↑ ↑ ↑

Cl Cl Cl Cl Cl Cl
Hybridization = sp3d2
Magnetic nature = paramagnetic
Outer orbital complex or high spin complex
Shape = Octahedral

Crystal field theory: - It is based on the assumption that the metal ion and the ligands acts as
point charges and the interaction between them are purely electrostatic.
In case of free metal ion all the five d- orbitals have the same energy. These orbitals
having the same energies are called degenerate orbitals.
“The conversion of five degenerate d- orbitals of the metal ion into different sets of
orbitals having different energies in the presence of electrical field of ligands is called crystal
field splitting.”
The ligand which causes only a small degree of crystal field splitting are called
weak field ligands while those which causes a large splitting is called strong field ligands.
In case of octahedral complexes the five d- orbitals split up into two sets ; one set
consist of two orbitals dx2 – y2 & dz2 of higher energy and called “eg-set” while the another set
consisting of three orbitals dxy dyz & dzx of lower energy and called t 2g-set as below:
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 Coordination Compound
eg-set

3/5∆o ∆o crystal field-

Average energy of 2/5∆o splitting energy

d-orbitals in a
d-subshell
t2g-set

d-orbitals in free state

The energy difference between the two sets of energy levels is called crystal field splitting energy. The
three orbitals lie at an energy that is 2/5Δ0 below the average d- orbitals energy and two d- orbitals lie at
energy 3/5Δ0 above the average energy.
The tetrahedral field splitting: -
t2g-set

2/5∆t ∆t crystal field-

Average energy of 3/5∆t splitting energy

d-orbitals in a
d-sub shell
eg-set

d-orbitals in free state

The energy difference between these two sets is called crystal field splitting in tetrahedral field &
is abbreviated as Δt.
It has been observed that the splitting in tetrahedral complex (Δt) is considerably less than
in octahedral complex (Δ○) it has been found that.

Δt = 4/9Δ○

Werner’s theory:- It explain primary & secondary valency.

i. Primary valency: -Primary valency is the main valency or ionic valency which is equal to
oxidation state of metal ion. And it is represented by doted line.
ii. Secondary valency: - secondary valency is the non- ionic valency. This is equal to co–ordinate
no. and it represented by dark line
e.g., [Cu (NH3)4]+2 SO4-2 pri. valency = +2 sec. valency = +4

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 Coordination Compound
Organometallic compounds – (OMC):- Organometallic compounds are those compounds which
contains one or more metal carbon bonds e.g. R-Mgx.
Organometallic compounds are of three types: -
a. Sigma (σ) bonded OMC
b. Pi (Π) bonded OMC
c. σ & Π-bonded OMC

i. Sigma bonded (σ) OMC:- Those compounds which contain metal carbon covalent bond
are called σ - bonded OMC
e.g. Grignard reagents (R – Mgx) i.e., CH3MgBr, C2H5MgBr etc.

ii. Π-bonded OMC: - that compound which contains metal carbon double bond are called Π
bonded OMC. “In these compounds the d- orbital of transition metal and Π orbital of
unsaturated hydrocarbon form a Π – bond due to the back bonding phenomenon.”
e.g. zeise’s salt – K [ PtCl3(C2H4)] H2C
Cl _

CH2
K+ Pt

Cl Cl

e.g. Ferrocene – Fe (ŋ5 – C5 H5)2

Fe

e.g. Dibenzene chromium – Cr (ŋ6 – C6H6)2

Cr

iii. σ - & Π-bonded OMC: - Metal carbonyl which contains both σ - & pi-bonded are
known as sigma- & pi-bonded OMC.
e.g., Ni (CO)4 , Fe(CO)5, Cr(CO)6, Mo(CO)6 etc.

 Monocentral carbonyl compounds: -compounds contain one CMI

e.g., Ni(CO)4, Fe(CO)5, Cr(CO)6
 Polycentral carbonyl compounds: - It means more than one metal ion are present in
these compounds.
e.g., Fe2(CO)9 , Fe3(CO)12, Mn2(CO)10
Note: - Chromium does not form polycentral carbonyl compounds.
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 Coordination Compound
Determination of no. carbonyl gp in compounds: - It is determine with the help of effective
atomic numbers (EAN). The EAN of the CMI is never greater than the
atomic number of next corresponding inert gas.

E.A.N = Z – O.S + x (no. of ligands)

Where Z = atomic no.

O.S = oxidation state
X for monodentate = 2 , Bi = 4, tri = 6 & for hexa = 12
e.g., [Ni (CN)4]-2 EAN = 28 – 2 + (2 x 4) = 34
Ni(CO)4 EAN = 28 – 0 + 8 = 36
Fe(CO)5 EAN = 26 – 0 +10 = 36

Stability of complex compounds: - Stability depends upon (a) nature of CMI

(b) nature of ligands
a. Nature of CMI: -
 Stability directly proportional to K (equilibrium const)

 Charge on CMI:- Stability directly proportional to charge on CMI in complex compounds.

 Size of CMI: - Stability α 1/size.

i.e., as the size of CMI decreases the stability increases.

 Chelate effect: - The stability also depends upon the formulation of chelate rings. This
distribution due to the chelation is called chelate effect. It is more stable
than normal complex compound.

 Macro cyclic effect: - When a polydentate ligand form cyclic stability & there are no
unfavorable stearic effect the complexes formed are more stable than
normal compound. This is called macro cyclic effect.

b. Nature of ligands: -
 Basic strength: - The more basic is a ligand, the greater is its tendency to donate its lone
pairs of electrons and hence greater is the stability of the complex
compound.
 Size and charge on ligands: - The higher is the charge and the smaller is the size the more
stable is the complex formed.

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Answers-

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