Some Important terminologies

● Coordination Entity/Coordination Sphere : It constitutes a

central atom/ion and ligand.

● Central Atom/Ion : The atom/ion around which a fixed

number of ligands are bound.

● Ligands : neutral molecules, anions or cations which are

directly linked with central metal atom or ion in the
coordination entity
Some Important terminologies

● Coordination Number : no. of 𝞼 bonds between the ligands

and the central atom/ion.

● Oxidation Number : Charge on central atom if all the ligands

are removed
 Some Important terminologies

Coordination
sphere

K4 Fe(CN)6
Ionisation sphere

Ligand

Central metal atom/ion

 Types of Ligand

● Monodentate : They have one donor atom, i.e they provide

only one e- pair to central metal atom or ion. Example : F-,
Cl-, Br-, H2O, NH3, CN-, NO2-

● Bidentate : They have two donor atom and have the ability
to link with central metal ion at two positions.

Example:-

H H -O O-
H 2C N
H 2C N C C
H H O O
Ethylenediamine(en) Oxalate(ox)
 Types of Ligand

● Tridentate : ligands having three donor atoms

Example:-

H
H
H N N H
H 2C CH2
H 2C N CH2
H
Diethylene triamine (Dien)
 Types of Ligand

● Tetradentate : ligands having three donor atoms

Example:-

H H
| |
N (CH2)2 N
(H2C)2 (CH2)2
N N
H | | H
H H
Triethylenetetramine (Trien)
 Types of Ligand

● Pentadentate : Posses five donor atoms.

Example:-

O- C O
O
-
O C O O- C CH
2
CH N (CH2) N CH2
2 H 2
Ethylenediamine triacetato ion (EDTA)3-
 Types of Ligand

● Hexadentate : Posses six donor atoms.

Example:-

H2 H2
N C C N
CH2 CH2
H2C O C O
-
O C
- O CH2
C O -
O C
-

=
O O
Ethylenediaminetetraacetate ion (EDTA)4-
 Types of Ligand

● Ambidentate Ligands: They can ligate through two

different sites present in it. Examples : CN-, NO2- and
SCN¯ ions

Example:-

O
M N M O N O
O
Nitrito - N Nitrito - O
 Types of Ligand

● Chelating ligand :- When a polydentate ligand is

bonded with MA from one or more donor atoms, then
the resulting structure is a 5- or 6- membered ring
structure, then the ligand is known as chelating ligand

O O- O
C C O
-
bidentate Mn+
C C O
O- -
O O
Sum of oxidation state (magnitude) and coordination number of cobalt in
Na[Co(bpy)Cl4] is

JEE Mains 2022

Solution:

Na [Co(bpy)Cl4]

Oxidation state of cobalt = + 3

Coordination number of cobalt = 6 [As bpy is bidentate]

Sum = 9
Nomenclature of coordination compounds

● Cation is named first in both positive and negative charged

coordination entities

● Ligands are named in an alphabetical order (according to the

name of ligand, not the prefix) before the name of the central
atom/ion.

● Names of the anionic ligands end in ‘o’

● Name of neutral ligands are the same except aqua for H2O,
ammine for NH3, carbonyl for CO, thiocarbonyl for CS and nitrosyl
for NO.
Nomenclature of coordination compounds

● Prefixes mono, di, tri, etc., are used to indicate the number of the
one kind of ligands in the coordination entity. When name of
ligand already include numerical prefix then bis, tris, tetrakis
are used

● Oxidation state of central atom should be written in roman

numeral in parentheses
Nomenclature of coordination compounds

● If the complex ion is a cation. The metal is named same as the

element. If the complex ion is an anion, the name of the metal
ends with the suffix - ate. For example. Co in a complex anion,
[Co(SCN)4] is called cobaltate. For some metals, the Latin
names are used in the complex anions, e.g., ferrate for Fe.

● The neutral complex molecule is named similar to that of the

complex cation.
Write the IUPAC name for the following:

Compounds IUPAC Names

Sodium tetrafluoridodihyroxochromate
Na3[Cr(OH)2F4]
(III)

Pentaaquachloridochromium (III)
[Cr(H2O)5Cl]Cl2
chloride.

Pentaaminethiocyanato - S - Chromium
[Cr(NH3)5SCN]Cl2
(III) chloride

[Pt(NH3)4Cl2] Tetraamminedichloridoplatinum (IV)

[PtCl4] tetrachloridoplatinate (II)
Q- As per IUPAC nomenclature, the name of the complex
[Co (H2O)4(NH3)2]Cl3 is :

A Tetraaquadiaminecobalt (III) chloride

B Tetraaquadiamminecobalt (III) chloride

C Diaminetetraaquacobalt (III) chloride

D Diamminetetraaquacobalt (III) chloride

Q- As per IUPAC nomenclature, the name of the complex
[Co (H2O)4(NH3)2]Cl3 is :

A Tetraaquadiaminecobalt (III) chloride

B Tetraaquadiamminecobalt (III) chloride

C Diaminetetraaquacobalt (III) chloride

D Diamminetetraaquacobalt (III) chloride

 EAN Rule

● Effective atomic number

E.A.N. = Atomic number - oxidation number + coordination number x 2

According to sidgwick the complexes in which the EAN of

the central atom equals the atomic number of the next
noble gas, are found to be extra stable.
 EAN Rule

Example: -

[Cr(CO)6]

Oxidation state of Cr = 0

E.A.N. = 24 - 0 + 6 x 2 = 36 (Atomic number of the next noble gas = Kr )

Note:- The EAN rule is not valid in all complexes but must be valid
for metal carbonyls [M(CO)x ]
 EAN Rule

Complex O.N. (metal) Atomic no. of Coordination E.A.N

Metal number

K4[Fe(CN)6] +2 26 6 26 - 2 + 6 x 2 = 36(Kr)

[Co(NH3)6]Cl3 +3 27 6 27 - 3 + 6 x 2 = 36 (Kr)

Ni(CO)4 0 28 4 28 - 0 + 4 x 2 = 36 (Kr)

K2[PtCl6] +4 78 6 78 - 4 + 6 x 2 = 86 (Rn)
Q- Which of the following is an oxidizing agent?

A Mn(CO)5

Fe(CO)5
B

C Mn2(CO)10

D Fe2(CO)9
Q- Which of the following is an oxidizing agent?

A Mn(CO)5

Fe(CO)5
B

C Mn2(CO)10

D Fe2(CO)9
Solution:

Mn(CO)5 + e ⟶ [Mn(CO)5]-
Less stable more stable, as EAN of Mn = 36(Kr)
 Werner’s Theory

● Elements show two types of valency :

○ Primary valency

○ Secondary valency
 Werner’s Theory

Primary Valency

● It corresponds to O.S of the metal atom/ion Cu2+, Fe3+, Co2+, Fe2+

● It’s also called principal, ionizable or ionic valency

● Its satisfied by anion

● These are non-directional in nature

 Werner’s Theory

Secondary Valency

● Its also known as coordination number(C.N)

● It is fixed for a metal
● Its non-ionizable & hence directional in nature
● Its satisfied by either anions or neutral molecules (e- pair
donor)
Q- The secondary valency and the number of hydrogen bonded water molecule(s)
in CuSO4.5H2O, respectively, are :

A 6 and 4

B 4 and 1

C 6 and 5

D 5 and 1
Q- The secondary valency and the number of hydrogen bonded water molecule(s)
in CuSO4.5H2O, respectively, are :

A 6 and 4

B 4 and 1

C 6 and 5

D 5 and 1
Solution:
 Valence Bond theory

● According to this theory, the metal atom or ion under the

influence of ligands can use its (n-1)d, ns, np, nd orbitals
for hybridisation to yield 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
 Valence Bond theory

Coordination Type of Hybridisation Distribution of hybrid

Number orbitals in space.

4 sp3 Tetrahedral

4 dsp2 Square planar

6 sp3d2 Octahedral

6 d2sp3 Octahedral
Valence Bond Theory (CN=4)
 Valence Bond Theory (CN=4)

Example - [NiCl4] 2– ( Paramagnetic)

 Valence Bond Theory (CN=4)

Example - [NiCl4] 2– ( Paramagnetic)

 Valence Bond Theory (CN=4)
Example - [Ni(CN)4] 2– ( Diamagnetic)
 Valence Bond Theory (CN=4)
Example - [Ni(CN)4] 2– ( Diamagnetic)
Valence Bond Theory (CN=6)
 Valence Bond Theory (CN=6)

Example: [Co(NH3)6] 3+ (diamagnetic)

 Valence Bond Theory (CN=6)

Example: [Co(NH3)6] 3+ (diamagnetic)

 Valence Bond Theory (CN=6)

Example: [CoF6] 3 (Paramagnetic)

 Valence Bond Theory (CN=6)

Example: [CoF6] 3 (Paramagnetic)

 Limitation of VBT

● It involved number of assumptions.

● It does not give quantitative interpretation of magnetic data.

● It does not explain the colour exhibited by coordination compounds.

● It does not give a quantitative interpretation of the thermodynamic or

kinetic stabilities of coordination compounds.

● It does not make exact predictions regarding the tetrahedral and square-
planar structures of 4-coordinate complexes.

● It does not distinguish between strong and weak ligands.

Q- The magnetic moment of an octahedral homoleptic Mn(II) complex is 5.9 BM.
The suitable ligand for this complex is :

A CN-

ethylenediamine
B

C NCS-

D CO
Q- The magnetic moment of an octahedral homoleptic Mn(II) complex is 5.9 BM.
The suitable ligand for this complex is :

A CN-

ethylenediamine
B

C NCS-

D CO
Solution:

The magnetic moment of the magnitude 5.9 BM suggest the presence of 5

unpaired electrons in Mn(II). This can be cross verified by putting the value
(5) of unpaired electrons in the formula, μ = √(n(n + 2)) BM Thus, the
valence electronic configuration of Mn(II) in the complex is :

The octahedral homoleptic complex suggests sp3d2 hybridisation in the

complex, i.e

Thus, 5 unpaired electrons are present in the complex which suggest the
presence of a weak ligand like NCS- .
The difference between spin only magnetic moment value of [Co(H2O)6]Cl2 and
[Cr(H2O)6]Cl3 is _________.
JEE Mains 2022
Solution:
Q- Match each set of hybrid orbitals from LIST-I with complex(es) given in LIST-II.
LIST-I LIST-II
(P) dsp2 (1) [FeF6]4–
(Q) sp3 (2) [Ti(H2O)3Cl3]
(R) sp3d2 (3) [Cr(NH3)6]3+
(S) d2sp3 (4) [FeCl4]2–
(5) Ni(CO)4
(6) [Ni(CN)4]2–
The correct option is

A P-5 ; Q-4,6; R-2,3; S-1

B P-5,6; Q-4 ; R-3 ; S-1, 2

C P-6; Q-4,5; R-1; S-2, 3

D P-4,6 ; Q-5,6; R-1,2 ; S-3

Q- Match each set of hybrid orbitals from LIST-I with complex(es) given in LIST-II.
LIST-I LIST-II
(P) dsp2 (1) [FeF6]4–
(Q) sp3 (2) [Ti(H2O)3Cl3]
(R) sp3d2 (3) [Cr(NH3)6]3+
(S) d2sp3 (4) [FeCl4]2–
(5) Ni(CO)4
(6) [Ni(CN)4]2–
The correct option is

A P-5 ; Q-4,6; R-2,3; S-1

B P-5,6; Q-4 ; R-3 ; S-1, 2

C P-6; Q-4,5; R-1; S-2, 3

D P-4,6 ; Q-5,6; R-1,2 ; S-3

Solution:
Postulates of Crystal Field Theory

● The metal-ligand bond to be ionic arising purely from

electrostatic interaction

● Ligands are treated as point charges in case of anions or dipoles

in case of neutral molecules.

● Five d orbitals in an isolated gaseous metal atom/ion have

same energy. ( degenerate )

● Because of unsymmetrical field of ligands the degeneracy of the

d orbitals is lost and cause splitting of the d orbitals.

● The pattern of splitting depends upon the nature of the crystals

field.
Crystal field splitting in Octahedral coordination entities
Crystal field splitting in Octahedral coordination entities
Crystal field splitting in Octahedral coordination entities
Crystal field splitting in Tetrahedral coordination entities
Crystal field splitting in Tetrahedral coordination entities
Crystal field splitting in Tetrahedral coordination entities
 Spectrochemical series

● Ligands can be arranged in a series in the orders of

increasing field strength.

I-< Br-< SCN-< Cl-< S2-< F-< OH-< C2O42-< H2O < NCS-< edta4-
< NH3 < en< CN-< CO

● It is an experimentally determined series based on the

absorption of light by complexes with different
ligands.

● Strong field ligand absorb high energy (smaller

wavelength)
 Crystal Field Theory

● Weak field ligand absorb low energy (greater wavelength)

1
Splitting energy ∝ Δabs ∝
λabs

● Crystal Field Splitting energy,(Δo) – Energy separation between t2g and eg

● Pairing Energy (P) – Energy required for electron pairing in single orbital
Crystal Field theory
 Crystal Field Stabilisation energy

CFSE = [- 0.4 (n) t2g + 0.6 (n’) eg ] Δo + *nP

n = no. of electrons in t2g

n’ = no. of electron in eg

Δo = crystal field splitting energy for octahedral complex.

*n = number of extra electron pairs formed because of the ligands in

comparison to normal degenerate configuration.
Q- Which of the following complex ions has electrons that are symmetrically filled
in both t2g and eg orbitals?

A [FeF3]3-

[Mn(CN)6]4-
B

C [CoF6]3-

D [Co(NH3)6]2+
Q- Which of the following complex ions has electrons that are symmetrically filled
in both t2g and eg orbitals?

A [FeF3]3-

[Mn(CN)6]4-
B

C [CoF6]3-

D [Co(NH3)6]2+
Solution:
Consider the following metal complexes:
[Co(NH3)6] 3+
[CoCl(NH3)5] 2+ JEE Mains 2022
[Co(CN)6] 3–

[Co(NH3)5(H2O)] 3+
The spin-only magnetic moment value of the complex that absorbs light with shortest wavelength
is _______ B.M. (Nearest integer)
Solution:

Stronger the ligand, higher the crystal field splitting.

[Co(CN)6] 3– > [Co(NH3)6] 3+ > [Co(NH3)5(H2O)]3+ > [CoCl(NH3)5] 2+

Higher the CFSE shorter will be wavelength

Co(CN)63-
Q- Homoleptic octahedral complexes of a metal ion ‘M3+’ with three monodentate
ligands L1, L2 and L3 absorb wavelengths in the region of green, blue and red
respectively. The increasing order of the ligand strength is:

A L3 < L1 < L2

B L3 < L2 < L1

C L1 < L2 < L3

D L2 < L1 < L3
Q- Homoleptic octahedral complexes of a metal ion ‘M3+’ with three monodentate
ligands L1, L2 and L3 absorb wavelengths in the region of green, blue and red
respectively. The increasing order of the ligand strength is:

A L3 < L1 < L2

B L3 < L2 < L1

C L1 < L2 < L3

D L2 < L1 < L3
Solution:

Lesser the wavelength of light absorbed (more energy) greater will be ligand
strength.
Energy: Blue > Green >
Red
Ligand strength: L2 > L1
> L3
 Organometallic compounds

Metal carbonyls - Compounds of metals with CO as a ligand.

They are of two types- Monomeric and polymeric

Monomeric - Metal carbonyls which contain only one metal atom per molecule
 Organometallic compounds

Polymeric - Metal carbonyls which contain two or more than two metal atoms per molecule
and they have metal-metal bonds
Synergic Bonding in metal carbonyl
Synergic Bonding in metal carbonyl

● The M-C σ bond is formed by the donation of lone pair of electrons

on the carbonyl carbon (CO is a weak base) into a vacant orbital of
the metal.

● The M-C 𝜋 bond is formed by the donation of a pair of electrons from

a filled d orbital of metal into the vacant antibonding 𝜋* orbital of
carbon monoxide.

● Carbon monoxide acts as donor (OC →M) and a 𝜋 acceptor

(OC←M), with the two interactions creating a synergic effect which
strengthens the bond between CO and the metal.
Q- Correct sequence of CO bond order in given compounds is :
(P) Fe(CO)5 (Q) CO
(R) H3B⬅CO (S) [Mn(CO)5]-

A P>R>S>Q

B S>P>R>Q

C Q>S>P>R

D R>Q>P>S
Q- Correct sequence of CO bond order in given compounds is :
(P) Fe(CO)5 (Q) CO
(R) H3B⬅CO (S) [Mn(CO)5]-

A P>R>S>Q

B S>P>R>Q

C Q>S>P>R

D R>Q>P>S
Solution:

CO bond order ∝

Correct sequence of CO bond order :

H3B ⬅CO > CO > Fe(CO)5 > [Mn(CO)5]-
(Co bond order >3.0) B.O. = 3.0 CO bond order < 3.0 (CO bond order < 3.0
Q- In the isoelectronic series of metal carbonyl, the CO bond strength is expected
to increase in the order.

A [Mn(CO6]+ < [Cr(CO)6 < [V(CO)6]-

B [V(CO)6]- < [Cr(CO)6 < [Mn(CO6]+

C [V(CO)6]- < Mn(CO6]+ < [Cr(CO)6

D [Cr(CO)6 < [Mn(CO6]+ < [V(CO)6]-

Q- In the isoelectronic series of metal carbonyl, the CO bond strength is expected
to increase in the order.

A [Mn(CO6]+ < [Cr(CO)6 < [V(CO)6]-

B [V(CO)6]- < [Cr(CO)6 < [Mn(CO6]+

C [V(CO)6]- < Mn(CO6]+ < [Cr(CO)6

D [Cr(CO)6 < [Mn(CO6]+ < [V(CO)6]-

Solution:

In the isoelectronic series of metal carbonyl, the CO bond strength is expected to

increase in the order [V(CO)6]−<[Cr(CO)6]<[Mn(CO)6]+
The oxidation state of the central metal atom increases in the order
V(−)<Cr(0)<Mn(+) .
As the oxidation state of the central metal atom increases, less and less electron
density is donated to the carbonyl ligand. This increases the CO bond strength as the
added electron density occupies the anti bonding orbital.
 Isomerism

Isomerism

Structural isomerism Stereoisomerism

Ionization isomerism
Geometrical isomerism

Hydrate isomerism
Optical isomerism
Linkage isomerism

Coordination isomerism
 Structural Isomerism

● Ionisation isomerism: when the counter ion in a complex salt

is itself a potential ligand and can displace a ligand which
can then become the counter ion.

Example:
[Co(NH3)5SO4]NO3 and [Co(NH3)5 NO3]SO4

● Hydration isomerism: Due to presence of different number of

water molecule inside a coordination sphere.

Example:
[Co(NH3)4Cl2]Cl.H2O and [Co(NH3)4 (H2O)Cl]Cl2.
 Structural Isomerism

● Coordination isomerism: Arises from the interchange of ligands

between cationic and anionic entities of different metal ions
present in a complex.

[Cu(NH3)4][PtCl4] and [Pt(NH3)4][CuCl4]

● Linkage isomerism: isomerism arises in a coordination

compound containing ambidentate ligands like NO2-, CN- , SCN-

[Co(NH3)4(NO2)Cl]+ and [Co(NH3)4 (ONO)Cl]+

 Stereoisomerism

Geometrical Optical
Isomerism Isomerism
Geometrical isomerism (CN=4)

❏ Tetrahedral Complex

Tetrahedral compounds can not show geometrical

isomerism because all four positions are equivalent in
tetrahedral geometry.
Geometrical isomerism (CN=4)

❏ Square Planar (Ma2b2)

Complexes with general formula , Ma2b2 (where a and

b are monodentate ligand) shows two isomers one
cis and one trans.
Geometrical isomerism (CN=4)

❏ Square Planar (Mabcd)

Mabcd type (where a,b,c,d are monodentate ligand) shows

three isomers two cis and one trans.
Geometrical isomerism (CN=6)

❏ Octahedral complex (Ma4b2)

Ma4b2 type (where a,b are monodentate ligand) shows two

isomers one cis and one trans.
Geometrical isomerism (CN=6)

❏ Octahedral complex (Ma3b3)

Ma3b3 type (where a,b are monodentate ligand) shows two

isomers one facial (fac) and one meridional (mer).

Example [Co(NH3)3(NO2)3]
Geometrical isomerism (CN=6)

❏ Octahedral complex (M(AA)2 a2)

M(AA)2a2 type (where a is monodentate and AA bidentate

ligand) shows two geometrical isomers are possible.

Example - [CoCl2(en)2]
 Optical isomerism (CN=4)

❏ Tetrahedral complex (Mabcd)

Mabcd type where a,b,c and d are monodentate ligand

For example - [As(III)(CH3)(C2H5)(S)(C6H4COO)]2+

 Optical isomerism (CN=4)

❏ Square Planar Complex

● Square planar complexes are rarely found to show the

optical isomerism.

● The plane formed by the four ligating atoms and the metal
ion is considered to be a mirror plane and thus prevents the
possibility of chirality.
 Optical isomerism (CN=6)

❏ Octahedral Complex

Optical isomerism is common in octahedral complexes

involving bidentate ligands due to absence of elements of

symmetry in the complex.

Example - [Co(en)3] 3+
 Optical isomerism (CN=6)

❏ Octahedral Complex

Example -[Pt(en)2Cl2] 2+

Only cis isomer show optical Trans isomer of does not show optical isomerism
isomerism
because presence of plane of symmetry
Q- Due to the presence of ambidentate ligands coordination compounds show
isomerism. Palladium complexes of the type [Pd(C6H5)2(SCN)2] and
[Pd(C6H5)2(NCS)2] are

A linkage isomers

B coordination isomers

C ionisation isomers

D geometrical isomers
Q- Due to the presence of ambidentate ligands coordination compounds show
isomerism. Palladium complexes of the type [Pd(C6H5)2(SCN)2] and
[Pd(C6H5)2(NCS)2] are

A linkage isomers

B coordination isomers

C ionisation isomers

D geometrical isomers
Solution:

[Pd(C6H5)2(SCN)2]

[Pd(C6H5)2(NCS)2]

SCN ⟶Thiocynato

NCS ⟶ Isothiocynato

In both complexes Pd is coordinated by ambidentate ligands it shows linkage

isomerism.
Q- The complex, [Pt(py)(NH3)BrCl] will have how many geometrical isomers?

A 2

B 3

C 4

D 0
Q- The complex, [Pt(py)(NH3)BrCl] will have how many geometrical isomers?

A 2

B 3

C 4

D 0
Solution:

M (ABCD)type complex have three geometrical isomers as:

Q- The possible number of geometrical isomers for the complex
[CoL2Cl2 ]- (L = H2NCH2CH2O- ) is (are) ______ .
Solution:

5
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