Electromeric effect: The phenomenon of movement of electrons from one atom to

another in multibonded atoms at the demand of attacking reagent is called electromeric

effect. It is denoted as E-effect and represented by a curved arrow ( ) showing the
shifting of electron pair.

A B E
A B
Reagent polar

Important features of electromeric effect

1-it is a temporary effect.
2-it is brought into play instantaneously at the demand of the attacking reagent. However as
soon as the attacking reagent is removed, original electronic condition is restored.

Attacking Attacking
C O
C O
reaagent C O
reaagent
removed
3- The electromeric effect is of common occurrence during addition of polar reagents on
C=C, C=O and C=N bonds etc.
4- The effect involves the complete transfer of electrons.
5- There is a complete charge formation and ions are formed.

Type of electromeric effect- The electromeric effect is of two types

1- +E effect
2- E effect

1- +E Effect- When the transfer of electrons take place towards the attacking reagent, the
effect is called +E effect. The addition of acids to alkenes.

C C + H C C

H3C C CH2 + H H3 C CH CH3

H
Since, CH3 group is electron donating, the electrons are transferred in the direction shown.
The attacking reagent is attached to that atom on which electrons have been transferred.
2- E effect- When the transfer of electrons takes place away from the attacking reagent,
the effect is called E effect. Example, the addition of cyanide ion to carbonyl compounds.
 C O + CN C O

CN

The attacking reagent is not attached to that atom on which electrons have been
transferred.

Mesomeric effect- it is a special type of resonating effect in which a functional group

is bonded with unsaturated carbon atom & can visualized by various canonical form is
known as mesmeric effect or resonance effect . It is represented by the M or R.

H2 C C NH2 H2C C NH2

H H

H2 C NH2 H2 C NH2

In the above example the lone pair of electron moves towards unsaturated group or atoms.
The mesomeric effect is of two types.

1- +M effect- Atoms or functional groups which are conjugated to the unsaturated

carbon atoms and donate of its lone pair electron towards carbon atom are called +M effect.
These are as fallows

O O
NH2
< <
NHR NR2
<
OH
<
OR
<
NHCR
<
OCR
<
F
<
Br
<
Cl

Decreasing order of +M effect

In phenol, the -OH group shows +M effect due to delocalization of lone pair on oxygen atom
towards the ring. Thus the electron density on benzene ring is increased particularly on
ortho and para positions.

Hence phenol is more reactive towards electrophilic substitution reactions. The substitution
is favored more at ortho and para positions
2- 2- -M effect - Atoms or functional groups which are conjugated to the unsaturated
carbon atoms and pi bond electrons of moves towards atoms or functional groups are called
-M effect. These are as fallows
O
NO2
< < < <
SO3H CN CHO
< <
C O COOH
<
COOR C NH 2

Decreasing order of -M effect

The nitro group, -NO2, in nitrobenzene shows -M effect due to delocalization of conjugated
electrons as shown below.
Note that the electron density on benzene ring is decreased particularly on ortho and para
positions

This is the reason for why nitro group deactivates the benzene ring towards electrophilic
substitution reaction

Resonance-
There are so many structure of organic and inorganic compound which structure cannot be
represent by any single structure but written by More than one structure. But none of them
explains all the observed properties of the molecule. The solution is to write an average of
all the valid structures, which explains all the properties. This condition is usually referred to
as resonance or mesomerism or delocalization.
The representation of structure of a molecule as a average of two or more hypothetical
structures, which only differ by the arrangement of electrons but with same positions for
atoms is referred to as resonance.

Salient features of resonance:

1 The hypothetical structures with different arrangement of electrons but with identical
positions for atoms are called resonance structures or canonical forms or contributing
structures.
2 The resonance structures are only imaginary and the actual structure of the molecule is
considered as the hybrid of all the valid resonance structures.
Resonance hybrid: The weighted average of contributing structures is known as resonance
hybrid. It is considered as the actual structure.
3 The energy of resonance hybrid is always less than the energy of any of the contributing
resonance structure.
4 The resonance structures are formed (only on paper) due to delocalization of electrons and
not by changing the positions of atoms.
5 The delocalization of electrons is shown using curved arrows.
For example Structure of urea,

N
H2N NH2
I

1) It should be a diacidic base,

2) The bond length of C-N bond is equal to the normal C-N bond length and
3) No dipole moment since it is symmetrical.
However it is observed that:
1) Urea is a monoacidic base,
2) It has shorter than expected bond length for C-N bond and
3) It shows dipole moment.
Hence, to account for above observations, the actual structure of urea is represented as a
resonance hybrid of following resonance structure

I II III

N
HN NH
RESONSNCE HYBRID
The contributing structures are always shown to be linked by using double headed arrows (
).

EXAMPLES OF RESONANCE STRUCTURES

The following resonance structures can be written for benzene which are hypothetically
possible due to delocalization of electrons. The Kekule structures have more weightage
than Dewar structures.

I II III IV V
 Kekules structure Dewars structure

Resonance hybrid

The actual structure of benzene is thus shown to be the hybrid of these contributing
structures. The bond order of every C-C bond is 1.5 and hence the every C-C bond length is
reported to be same and equals to 1.39 Ao, which is in between the bond length values of C-
C single bond (1.54 Ao) and C=C double bond (1.20 Ao ).
Due to resonance, benzene gets extra stability and does not undergo electrophilic addition
reactions. However it shows electrophilic substitution reactions. This phenomenon is known
as aromaticity.
A resonance hybrid structure is more stable than of its resonating structure. The difference
between in the energy between the hybrid and most stable structure is known as
resonance energy. This energy difference is equal to 36 Kcal/ mole.

E2

Resonating structure
E1
E = 36 cal/mole

Resonance hybrid

Energy - structures diagram of Benzene

Application of resonance
1 The acidic character of acetylene can be explain on the basis of resonance theory-

H + C C H H C C H H C C H
Acetylene
2 The non reactivity of halogens in vinyl halide can be explain on the basis of resonance
theory -
 H2C C Cl H2C C Cl
H H
Vinyl chloride
3 The higher reactivity of halogen atom in alkyl halide is due to the fact that the ally lithium
ion gets stabilized by resonance.

H2
H2C C C Cl H2C C CH2 + Cl
H H

H2C C CH2 + Cl
H

4 The colour of dyes can be explain on the basis of resonance.