Electronic effects:

The effect which appears due to electronic distribution is called electronic effect.

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Similarly if the element is less electronegitive than carbon such as (Si) and attached to the carbon chain, then partial positive
charge developed on silicon atom and partial –ve charge developed on carbon atom as shown below.

Thus inductive effect may be defined as a permanent displacement of sigma electrons towards more
electronegitive atom
It can also be defined as polarisation of one bond caused by polarisation of adjacent bond.
It is also called transmission effect.
It causes permanent polarisation in molecule, hence it is a permanent effect.
The displacement of electrons takes place due to difference in electronegativity of the two atoms involved in
the covalent bond.
The electrons never leave their original atomic orbital.
Its magnitude decreases with distance and it is almost negligible after 3rd carbon atom.
The inductive effect is always operative through sigma bond, does not involve Π bond electron.
(Lets take an example of acetone, in acetone both Pi and sigma electrons will polarise due to difference in
electronegativity but we consider only sigma electrons under inductive effect)

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Types of inductive effects:
- I Effect : The atom or group which attracts the bond pair of electrons towards itself, more strongly than
hydrogen(H) known as -I atom/group and this effect is called -I effect. Various groups are listed in their
decreasing -I strength as follows.

+ I effect : The group which release electron cloud is known as + I group and effect is + I effect.

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Conjugation: Any system (molecule/ion/radical) is said to be conjugated if it has i) Π-bond and Π-bond, ii)
Π-bond and lone pair of electrons, iii) Π-bond and +ve charge, iv) Π-bond –ve charge, v) Π-bond and
unpaired electron, vi) lonepair of electron and +ve charge at alternate position

Π- Π conjugation: when two pi bonds are separated with single bond that system is said to be Π- Π
conjugation. If conjugation present in the molecule, conjugated electrons cant stay at one position, they keep
on moving around the molecules this is nothing but a delocalization of electrons.

Π-Π conjugation

Π-Π conjugation

No shifting of electrons

Π- -ve conjugation: when –ve charge separated from a Π- bond with single bond that system is said to be Π-
-ve conjugation.

Π- −ve conjugation

X
BR3 BR3
In this type of conjugation –Ve charge will migrate towards double bond Π- −ve conjugation
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Π- +ve conjugation: when +ve charge separated from a Π- bond with single bond that system is said to be
Π- +ve conjugation.

Π- +ve conjugation

X We should not write this kind of resonance, second row

N N elements never exceed octet

X We should not write this kind of resonance, second row

O O elements never exceed octet

Π- unpaired electron( radical) conjugation: when odd electron separated from a Π- bond with single bond
that system is said to be Π- radical conjugation.

Π- +ve conjugation

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Π- lone pair conjugation: when lone pair of electrons separated from a Π- bond with single bond that
system is said to be Π- lone pair conjugation.

Cl Cl

Note: if there is more than one lone pair is there only one lone pair involve in conjugation
In this type of conjugation lone pair migrates towards Pi bond

+ve- lone pair conjugation: when lone pair of electrons separated from a Π- bond with single bond that
system is said to be Π- lone pair conjugation.

O O O O

R O R C O R O R O

In this type of conjugation lone pair migrates towards +ve charge

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Resonance (mesomerism):
It has been found that, in the case of some molecules or ions no single structure is able to explain all the
properties of molecules.
2
Let me take an example benzenecyclic structure containing alternating C–C single and C=C 1 3
double bonds.

As per the given structure C1-C2 bond length must be different C2-C3 bond length, but in benzene ring all
the C-C bond legths are idetical which is 1.39Aº which is lower than C-C s=bond(1.54Aº) and higher than
C=C(1.34Aº)
So benzene can be represented equally well by the energetically identical structures I and II.

Therefore, according to the resonance theory the actual

structure of benzene cannot be adequately represented by
any of these structures, rather it is a hybrid of the two
structures (I and II) called resonance structures. Or
canonical forms
Resonance hybrid: Resonance hybrid is the avarage
structure of the resonance structures

H H

H H

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Acetate ion is the another example for resonance
H O

H
H O

Resonance hybrid

Resonance structures are not real, they are imaginary but resonance hybrid is real

Energy of the actual structure (resonance hybrid) of the molecule is lower than that of the any of the
canonical forms (resonance structures)

Stability of resonance hybrid is always higher than the corresponding resonance structures

Phenomena of the resonance is possible only if there is a conjugation

The only difference between resonance forms is the placement of the π and nonbonding valence electrons,
position of the nuclei should not change

Number of unpaired electrons should not change in the resonance structures

All atoms taking part in the resonance, that is, covered by delocalized electrons, must lie in a plane or
nearly so

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In fused six-membered aromatic rings, the principal canonical forms are usually not all equivalent. Below
compound has a central double bond and is thus different from the other two canonical forms of naphthalene,
which are equivalent to each other. For naphthalene, these are the only forms that can be drawn

Napthalene don’t have equivelent resonance structures like benzene

Q is C1-C2 and C2-C3 bond lengths are identical or different?, if it is different which is having longer bond
length?
Q write the number of possible resonance structures for anthracene and phenanthrene?

anthracene phenanthrene

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Draw the resonance structures for each of the following compounds

OH
NaOH
N

OH Na
OH NH3 OH2
N

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Resonance Energy or Resonance stabilization energy:

Resonence energy Calculation:

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Resonence energy of the benzene is calculated from the heat of hydrogenation:

+ H2 + 28.6 Kcal

+ H2 + 3 x 28.6 Kcal = 85.8 Kcal

this is expected value

But experimental value is 49.8 kcal

Resonance energy = Calculated value – Experimental Value = 85.8-49.8 = 36 kcal

The resonance energy may also be calculated using heat of combustion value

Resonance energy is a property of resonance hybrid not the property of resonance structure

Select the species having the identical resonance energy?

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Resonance or mesomeric effect:

Π-Π conjugation

Like inductive effect this is also permanent effect.

Resonance or mesomeric effect will be classified in to two types
i) +R or +M ii) –R or -M

-M effect or -R effect: If transfer of Π-bond electrons takes place from a conjugated system to a group is
known as -M effect that group is known as -M or -R group.

-NO2 > -CN > -SO3H > -CHO > -COR > -COOR > -COOH > CONH2

What kind groups can act as a –M groups?

The functional groups which is having polar multiple bonds can act as –M group

conjugated system
or Pi system
this is the group

O O O O

H H H H
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 O O
C N C N N O N O

Here CN is taking Π-electons from double bond Here NO2 is taking Π-electons from double bond

Now the question is why Pi electrons present in C=C will move towards the group, why Pi bond present in
the group not moving towards C=C?

H H
X Oxygen atom can not have +ve charge with single bond, but
O O
oxygen atom ca have +ve charge with three bonds.

X
C N N also also can not have +ve charge with two bonds, but it can have
C N +ve charge with f our bonds

Write the resonace structures for the below compounds

COCH3 NO2 CN SO3H

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+M effect or +R effect: Transfer of nonbonding electrons takes place from a group to a conjugated system
is known as +M effect that group is known as +M or +R group.

-O- > -NH2 > -NR2 > -OH > -OR > -NH-COCH3 > -O-COCH3 > -X (halogens)
** Ph group behaves as a +R group

What kind of groups can act as +M or +R groups?

The functional group which is having lone pair of electrons, the lone pair bust be in conjugation with Pi bond
or p orbital,

Conjugated system Group

NH2 NH2 NH2

NH2

But there are some groups which can act as a both +M as well as –M
Eg –NO, -SOR, -Cl

Write the resonance structures for the given molecules

OH NH2 O Cl

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9. Stability is decreased by an increase in charge separation. Structures with formal charges are less stable
than uncharged structures. Structures with more than two formal charges usually contribute very little. An
especially unfavourable type of structure is one with two like charges on adjacent atoms.

10. Structures that carry a negative charge on a more electronegative atom are more stable than those in
which the charge is on a less electronegative atom. Thus, II is more stable than I. Similarly, positive charges
are best carried on atoms of low electronegativity.

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Applications of mesomeric effect:
Bond length and bond strength:
Arrange the given molecules in increasing order of bond length and bond strength

Cl Cl Cl

i ii iii
In molecule i resonance is not possible C-Cl bond is 100% single bond
In molecule ii & iii n-Π conjugation is possible as shown below
Cl Cl Cl Cl Cl

Cl Cl

In molecule iii C-Cl double bond character is more than ii so

Boond length order is i > ii > iii; Bond strength order is iii > ii > i

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Steric Inhibition of Resonance and the Influences of Strain (SIR)
A per our previous discussion all the atoms covered by delocalized electrons must lie in a same plane.
Many examples are known where resonance is reduced or prevented because the atoms are sterically forced
out of planarity.
Bond lengths for the o- and p-nitro groups in picryl iodide are quite different. Distance a in 33 is 1.45A ° ,
whereas b is 1.35A ° . This phenomenon can be explained if the oxygens of the p-nitro group are in the plane
of the ring and thus in resonance with it, so that b has partial double-bond character, while the oxygens of the
o-nitro groups are forced out of the plane by the large iodine atom.

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There is another type of double bond that is particularly common for the second-row atoms, sulfur and
phosphorus.
it is formed by overlap of a filled p orbital from the oxygen with an empty d orbital from the either sulphur or
phosphorus sulfur.

amine oxides, analogs of phosphine oxides, can only be written R3N+ - O-. The ppi–dpi canonical form is
impossible since nitrogen is limited to eight outer-shell electrons.

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Cross Conjugation: In a cross-conjugated compound, three groups are present, two of which are not
conjugated with each other, although each is conjugated with the third.

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Electromeric effects:
It is a temporary effect. The organic compound having a multiple bond ( double or triple bond) show this
effect in the presence of an attacking reagent only. It is defined as the complete transfer of a shared pair of Pi-
electrons to one of the atoms joined by a multiple bond on the demand of an attacking reagent. It is
represented by E and the shifting on the electrons is shown by a curved arrow. There are two types of
eletromeric effect.

(i) +E effect : In this effect Pi-electron of the multiple bond are transferred to that atom to which the
reagent gets attached.

(ii) E effect : In this effect the Pi-electron of the multiple bond are transferred to that atom to which the
attacking reagent does not get attached.

When inductive and electromeric effects operate in opposite directions then the electromeric effect
dominates.

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 APPLICATIONS OF MESOMERIC EFFECT
It explains the stability of carbocation

Which is more stable?

in Allyl cation there are a two carbon atoms to share +ve charge

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 O
O
here electronegitive atom is getting +ve charge which is highly
1
H
H unstable

NH
NH
2 H
H

But here +ve charge was shated by both carbo atoms

3
H so this is more stable
H

the stability order of this carbo cations are 3>2>1

A B C D

what is the stability order of given carbo cation?B > A > C > D

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 Which is more stable?
O
I II

In structure - 1 resonance possible, carbo cation is nothing but a empty P orbital adjecent

oxygen is having a lone pair of electrons, so lone from oxygen will delocalize in to empty P orbital

O O O O
H

OH NH2 F Which is more stable?

I II III

II > I > III here in all cases resonance possible, but which is strong +M group

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 Which is more stable?
O S
I II

2P
2P

O O O O
H

2P-2P interaction better interaction

2P 3P

S
S S S

3P-2P interaction poor interaction

So stability order is 1 > 2

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 CH2 CH2
Which is more stable and why?

CH2 CH2 CH2 CH2 CH2

CH2 CH C
Stability order

I II III
III > II > I more the resonance structure more will be the stability

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 CH2
CH2 CH2 CH2
CH3

CH3
CH3
I II III IV

CH2 CH2 CH2 CH2 CH2

CH3 CH3 CH3 CH3 CH3

CH2 CH2 CH2 CH2 CH2

CH3 CH3 CH3 CH3 CH3

CH2 CH2 CH2 CH2 CH2

CH3 CH3 CH3 CH3 CH3

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 CH2
CH2 CH2 CH2
OCH3

OCH3
OCH3
I II III IV

CH2 CH2 CH2 CH2 CH2 CH2

OCH3 OCH3 OCH3

OCH3 OCH3 OCH3

CH2 CH2 CH2 CH2 CH2

OCH3 OCH3 CH2
OCH3 OCH3 OCH3 OCH3

CH2 CH2 CH2 CH2 CH2

OCH3 OCH3 OCH3 OCH3 OCH3

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 CH2
CH2 CH2 CH2
CHO

CHO
CHO
I II III IV

CH2 CH2 CH2 CH2 CH2

CHO CHO CHO CHO CHO

CH2 CH2 CH2 CH2 CH2

CH3 CHO CHO CH3 CH3

CH2 CH2 CH2 CH2 CH2

CHO CHO CHO CHO CHO

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 CH2
CH2 CH2 CH2
NO2

NO2
NO2
I II III IV

CH2 CH2 CH2 CH2 CH2

NO2 NO2 NO2 NO2 NO2

CH2 CH2 CH2 CH2 CH2

NO2 NO2 NO2 NO2 NO2

CH2 CH2 CH2 CH2 CH2

NO2 NO2 NO2 NO2 NO2

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It explain the stability of carbanion

Which is more stable?

in Allyl cation there are a two carbon atoms to share +ve charge

*** resonance stabilised carbanion is SP2 hybridization, isolated carbanion is SP3 hybridization

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 O
O
1 here electronegitive atom is getting -ve charge which is highly
H
H
stable
NH
NH
2 H
H

But here ve charge was shated by both carbo atoms

3
H so this is less stable
H

the stability order of this carbo cations are 1> 2> 3

A B C D

what is the stability order of given carbo cation? C > A > B > D

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 CH2 CH2
Which is more stable and why?

CH2 CH2 CH2 CH2 CH2

CH2 CH C
Stability order

I II III
III > II > I more the resonance structure more will be the stability

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 CH2
CH2 CH2 CH2
CH3

CH3
CH3
I II III IV

CH2 CH2 CH2 CH2 CH2

CH3 CH2 CH3 CH3 CH3

CH2 CH2 CH2 CH2 CH2

CH3 CH3 CH3 CH3 CH3

CH2 CH2 CH2 CH2 CH2

CH3 CH3 CH3 CH3 CH3

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 CH2
CH2 CH2 CH2
CHO

CHO
CHO
I II III IV

CH2 CH2 CH2

CH2 O CH2 O CH2
CHO CHO CHO CHO
H H

CH2 CH2 CH2 CH2

CH2 CH2

CHO CHO CHO

CHO
H O H O

CH2 CH2 CH2 CH2 CH2

CHO CHO CHO CHO CHO

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