' - E effect

Y==C^C== C
( Displacement towards group Y)

Again like inductomeric effect, since the elcctromeric effect takes place only at the requirement of the
attacking reagent it always facilitates the reaction and never inhibits it. The clectromeric effect is of common
occurrence during addition of polar reagents on C=C and C=0 bonds.
The combined mesomeric and electromeric effects of the atom or group is known as its conjugative
effect. Since the conjugative effect was first recognized in connection with the phenomenon of tautomerism,
it was previously known as the tautomeric effect ( T).

3.6 Resonance
It has been observed that a single structural formula of certain molecules, viz. benzene cannot
satisfactorily explain all the properties of the molecule. Such a compound can be represented by two or more
hypothetical electronic structures (arrived by redistribution of valence electrons in ionised or unsaturated
centres) each of which separately accounts for most, but not all, of its properties.
I
Each of the two structures has three carbon-carbon single bonds and three carbon-carbon double bonds, i.e.
they have two types of carbon-carbon bonds. But it has been experimentally determined that all carboncarbon bonds in benzene are identical and have the same bond length (1.39A). Furthermore, the carboncarbon bond length (1.39 A) in benzene is intermediate between the normal carbon-carbon double bond
length (1.33 A) and the normal carbon-carbon single bond length (1.54 A). Thus actually neither of the above
two structures is a correct representation of benzene.
It was, therefore, conceived that the true structure of the compound is an intermediate between two or
more valence structures- a sort of hybrid that cannot exactly be depicted on paper. The molecule in such cases
is said to be in a state of resonance (Heisenberg, 1926) or mesomerism (Ingold, 1933). Thus resonance may
be defined as the phenomenon in which two or more structures, involving identical position of atoms, can
be written for a particular compound.
As the structure of the actual molecule or the so called resonance hybrid cannot be depicted on paper,
its structure and properties are obtained by mentally combining the formulae and properties of the various
contributing forms. To indicate that two forms contribute to a resonance hybrid, a double headed arrow of the
type <>is placed between the two forms. Thus following the above concept of resonance theory, the
benzene molecule may be expressed as a resonance hybrid of the two contributing Kekule structures. Such
contributing structures are commonly known as canonical structures. Thus the canonical structures of a
system may be defined as any set of valency structures which are sufficient to define all the possible
electron distributions. An alternative representation of the benzene molecule, i.e. its hybrid structure,
involves a circle drawn inside of the benzene hexagon.

as the actual structure of all differentpossible structures that can be written for the
molecule without changing the relative position of its atoms and without violating the rules ofcovalence
maxima for the atoms. By way of analogy, a mule is a hybrid of a horse and a donkey. It is forever a mule, and does not alternate between being a horse and being a donkey. Thus it may be written "mule horse <
Thus we may now define resonance hybrid

> donkey" but never "mule = horse donkey"

.

Reactions and Reagents

Necessary conditions for resonance : Generally, a resonance hybrid will have more than two canonical
structures which ordinarily make unequal contributions to the hybrid, but out of all the possible contributing
forms, only the major contributing forms are used while representing a resonance hybrid. For
2
example, benzene is although regarded as a resonance hybrid of the following structures, only the first two

iv)
(iv)
(iii)
0 (vi)

structures are the major contributing forms since on theoretical grounds the diradical structures (iii) and (iv) and
the charged* structures (v) and (vi) are of less importance and make a smaller total contribution to the resonance
hybrid. The ability to pick out the major contributing forms is acquired by experience; however the following
principles provide the general guidance for selecting the major contributing forms for resonance hybrid of a
particular compound.
1. The major contributing forms arc of comparable energy. Thus from all the above contributing
structures for benzene, only the two Kekule structures (i) and (ii) have the same energy and thus constitute the
major contributing structures.
2. The nuclei in each of the canonical structures must be in the same relative positions. For example, the
structure (viii) does not contribute to the structure (vii) of isobutylene but is instead the isomeric compound,
/rans-2-butene.
CH3V
/H
y/CHj

CHJ'

CHJ

=C

\
(vii)

(viii)

3. The various resonating structures differ only in electron distribution and are obtained by a slight
displacement of electrons.
H

\ /H /

Ci:
H

CI :

4. All the resonating structures in a set must have the same number of paired and unpaired
electrons (although their positions may be different). For example, the following two structures of
ethylene are not
considered as the resonating structures because they do not contain the same number of paired electrons.
+

CH2=CH2
CH2CH2
Anyhow, if at all it happens, the structure having lesser number of paired electrons has a very minor

CH2-CH=CH-CH2
(iii)
contribution to the hybrid as in the case of butadiene.

CH2=CH-CH=CH2 <> CH2-CH=CH-CH2 (i) (")

Actually the type of resonance between (i), (ii) and (iii) is called as the heterovalent resonance.
5. In general, non-polar structures are more stable than the dipolar unless one atom is electropositive.
In case an ionic bond tends to be formed a dipolar structure is less stable than the corresponding non-polar
It must be noted that the higher energy (viz. diradical) and charge separated structures may be unimportant contributors to
the ground state of the molecule (as when the substance is stored in a dark bottle at room temperature), but may
become important in an activated state of the molecule, as during a chemical reaction or on irradiation with ultraviolet
light.
Copyrighted materia
l

by an amount of energy required to prevent coalescence or mutual annihilation of the opposite charges. Thus
in case of benzene, resonating structures (v) and (vi) are less stable than structures (i) and (ii). Similarly, in
the resonating structures of carboxylic acids, structure (ii) is less stable than the (i), although both of them
have the same number of bonds.
Furthermore, among the dipolar structures, farther apart the charges are, the less stable is the resonance form.
Thus among the resonating structures of butadiene, structures (iii) are the least stable followed by
(ii),
followed by the non-polar form (i) which makes the greatest contribution
to the resonance

hybrid.
**

CH2=CHCH=CH2 <> CH2=CHCHCH2 <> c h 2 - - C H = C H C H 2 (i) (ii) (iii)

6. Structures involving formal charges arc the most stable when the negative and positive charges
reside on the most electronegative and electropositive atoms respectively. Thus in case of ketones, the ionic
structure (ii) is more stable than the (iii). This rule can be visualised by observing the addition reactions of a
carbonyl group when the positive fragment of the addendum always adds to the oxygen atom which thus must
be negatively charged.
7. Structures with like formal charges on adjacent atoms have very high energy and are thus unstable.
8. Structures with electron-deficient positively charged atom have very high energy and are thus
unstable.
9. More the number of covalent bonds in a resonating structure more will be its stability. Since a
covalent bond has about 50-100 kcal/mole of energy it contributes about 50-100 kcal/mole to the stability of
the system, while the difference in stability of resonating forms is only a fraction of this amount, the
resonance structure with the greater number of covalent bonds will usually be the more stable. Thus among
the various possible resonating structures of benzene (sketched above) structures (iii) and (iv) are
comparatively less stable than the structures (i) and (ii) containing three double bonds.

Similarly, among the various resonating structures of carbonate ion, structure (iv) is less stable.
w.y.

/Hi obi
10. An essential requirement for resonance is that the resonating structure must be planar (or nearly
planar). Thus, if planarity is partially reduced or completely prevented by the steric effect of a group, resonance
is diminished or inhibited (steric inhibition of resonance).
Resonance energy : Since in the mesomeric structure electrons arc more delocaliscd than in any of the
individual canonical structure, it (mcsomeric structure or the resonance hybrid) will be more stable than any
of the individual canonical structure, including of course, the classical structure itself. For example, the total
energy of the benzine hybrid is lower than the total energy of the two classical Kckule structures by some 36
kcal/mole. The difference in energy between the hybrid and the most stable canonical
structure is referred to as the resonance energy of the molecule, and thus benzene is said to be stabilized by a
resonance energy of 36 kcal/mole. It is observed that larger the number of the possible canonical structures
greater will be the resonance energy and hence stability of the compound.
Resonance Energy of Benzene

Furthermore, resonance energy is quite large when the contributing forms have the same structural
feature e.g. benzene has a large resonance energy (36 kcal/mole). On the other hand, if the contributing forms
have widely different structural features (e.g. the case of chloromethane), the resonance energy of the hybrid
will be small.
The resonance energy may be determined experimentally by measuring heat of combustion or better by
heat of hydrogenation. The resonance energy of a resonance hybrid is the difference between the theoretical
and experimental heats of hydrogenation of the compound . For example, the resonance energy of benzene
can be determined from the following data.
Accordingly,
But, however, the observed heat of hydrogenation of benzene is 49.8 kcal/mole.
Therefore, benzene has 85.8-49.8 kcal/mole less energy than expected for a typical compound with three
double bonds. Hence resonance energy of benzene molecule in 85.8 -49.8 = 36.0 kcal/mole by which the benzene
molecule is stabilized. The stabilization (approximately resonance) energy of some of the common compounds
+ 3H
arc tabulated on the next page.

Table 3.7. Stabilization Energy1 (or Approximate Resonance Energy) from Heat of Combustion
(AH) of some Compounds

Benzene

827

789

38

It is important to note that stabilization and resonance energy arc not necessarily equal, bccausc the latter (R.E.) is due to the
stability gained by the derealization of electrons while the former (S.E.) is the net of all effects, both stabilizing and destabilizing.
1

Toluene

1597

1514

83

1540
983

1481
944

59
39

1250

71

1321

1279

42

1816

1712

104

1816

1705

111

696

675

21

Biphenyl

Biphenylene

O
Naphthalene
1321
Azulene

Anthracene

Phenanthrene

Pyridine
N

41

Aniline

OH

1
Phenol

789

749

40

1, 3-Butadiene

CH2=CH-CH=CH2

608

608

Nil

1, 3-Pentadienc

CH2 CH.CH=CH.CHJ

765

762

765

762

1103

1095

677

672

2-Methyl-l, 3-butadicne
(Isoprene)

===

CHJ

CHJCCHCH3
Cyclooctatetraene

Benzoquinone

Effect of resonance : The phenomenon of resonance causes several effects; physical (bond length, dipole
moment and stability of free radicals and carbonium ions) and chemical; on the properties of the molecules.
( i ) Dipole moment: In certain molecules, measured dipole moments can only be accounted for in terms
of resonance. For example, in vinyl chloride the existence of a certain amount of polarity in the bonds and thus
the dipole moment can only be explained if stnicture II contributes to the actual structure (resonance hybrid) of
the molecule.

CH2=CHCI
I

<> H2CCH=C1

dipole moment = 1.4 D

II

Similarly, the phenomenon of resonance also explains the measured dipole moments in cyanides,
isocyanides, carbonyl compounds, etc.
RC=N <> RC^ N ; R N =C 4> R N a C I II I II
Dipole moment due to dative bonds in structures II

824
865
(ii) Bond length ; The phenomenon of resonance explains the abnormal bond length between CC,
C=C, C=0, etc. in the compounds exhibiting resonance. Thus the concept ofresonance gives an explanation for
observed bond length being midway between a single and double bond viz. the distance between every two
adjacent carbon atoms in benzene is against the normal CC (1.54 A) and C=C (1.33 A) distances. Similarly,

the C-Cl bond length (1.72 A) is shorter in vinyl chloride than that in ethyl chloride (1.78 A). The explanation, in
general, is that the effected bond in the resonance hybrid is neither single nor double.

(iii) Strength of acids and bases: The concept of resonance explains clearly the acidic character of
acids, and basic character of bases. For example, resonance explains why the alcohols are neutral and
carboxylic acids are strong acids. The ionization of the molecules in the two cases is as follows.
But now since the carboxylate anion can undergo phenomenon of resonance in the following way, while the
aikoxide ion can't do
so, the former is stabilized*. Moreover, it should be noted that the resonance stabilization is more in
carboxylate ion as compared to the parent acid since in the latter case it is diminished due to the charge
separation.
Similarly, we can explain why the aromatic amines are weaker bases as compared to the aliphatic
amines. In case of aromatic amines viz. aniline the lone pair of electrons on the nitrogen atom is involved in
resonance and hence is lesser available for protonation as compared to aliphatic amines where the
phenomenon of resonance is not possible and hence lone pair of electrons is very easily available for
protonation.
(/v) Stability of free radicals and carbonium ions : The following relative order of stability of free
Tertiary > Secondary > Primary

radicals is explained on the basis of resonance theory. Thus the tertiary free radical (or carbonium ion) is the
most stable since here the odd electron can delocalize over the central carbon atom and nine other positions (6
ortho + 3 para) of the three phenyl groups. In general, greater the number of resoualiug structures of a species, higher
will be its stability.

Similarly, the relative stability of the carbonium ions (tertiary > secondary > primary) can be explained.
(v) Conjugate addition to dienes : When one moles of a reagent capable of adding to an alkene reacts
with a conjugated diene, two products are formed, a normal 1 9 2-addition product and an abnormal 1, 4addition product, e.g.
The formation of the 3,4-dibromo compound is not surprising, since it is the result of normal addition to an
individual double bond. The formation of the 1,4-dibromo compound, which is often the major one f is said to
arise by conjugate addition to the diene. Conjugate addition is explained in terms of resonance theory as
illustrated in the following two-steps bromination mechanism. In the first step a carbonium ion is formed as
usual.
Out of the above two possible carbonium ions, since the secondary carbonium iota is more stable, further
addition i.e. the second step will be taking place on the secondary carbonium ion. Now since the secondary
carbonium ion is a resonance hybrid of the two canonical structures, it may be attacked by Br~ at either of its
centres of maximum electron deficiency to give products of both normal and abnormal conjugate addition.

Table 3.8 Difference between resonance and tautomerism*

'

1. The various contributing structures do not exist in

reality. The phenomenon gives idea of single
molecular structure.
2. There is slight displacement of electrons. Ail the
atomic nuclei must occupy the same position in all
the contributing structures.
.

See also chapter on tautomerism.

1. The two forms exist in dynamic equilibrium with

each other and hence can be isolated.
Tautomerism involves migration of atomic nuclei

2.
3. Resonance affects the bond lengths, i.e., the single bond is shortened while the double bond becomes
lengthier.
4. Resonance stabilizes the molecule by lowering its energy.
5. Resonance occurs only in the planar molecules.
6. The structure of the various resonating structures is similar.
7. Resonance is represented by inserting the double headed arrow (<>) between the contributing structures.
3. Tautomerism has no effect on bond lengths.

4. Tauotmerism docs not lower energy of the molecule.

5. There is no such condition in tautomerism.
6. The two tautomeric forms have different structures, i.e., different functional groups.
4. Tautomerism is represented by inserting reversible arrow (

between the two tautomers.

3.7 Hyperconjugation
Baker and Nathan in 1935, while investigating the mechanism of the reaction betweenp-substituted benzyl bromide and pyridine observed that the reaction rate increases as the electronegativity of the group
X

\ //
decreases. In other words if the group X is capable of withdrawing electrons (i.e. -1 group, viz. - N02 group)
from the benzene ring, 0 2 N C , reaction slows up; while the opposite group (i.e. +1 group viz. -Cii3 group,
H30>~C) speeds it up. Now since the inductive effect of the various alkyl groups follows the following order,
Me3C > MejCH > CH3CH2 > CH3
the reaction rate should also increase in the same order when X is substituted by these alkyl groups. But actually
the two workers found exactly the opposite reaction rate which coincided with the above order.
CH3 > H3C.CH2 > (CH^CH > (CH3)JC
It thus appears that the alkyl groups are capable of giving rise to electron release by a mechanism, different from
the inductive effect, in which methyl group is the most successful exponent while the /er/-buty 1 group is the
least.
Baker and Nathan suggested that alkyl groups with at least one hydrogen atom on the a-carbon atom
when attached to an unsaturated carbon atom are able to release electrons by a mechanism similar to that of the
electromeric effect, e.g.
H
Note that this type of delocalisation involves a- and /r-bond orbitals (or /7-orbitaIs in case of free radicals), thus it is also known as G-n conjugation. This type of electron release due to
the presence of the system HCC=C is known as hyperconjugation. More the number of HC bonds attached to the unsaturated system more will be the probability of
electron release by this mechanism. Thus the electron release by this mechanism will be greater in methyl (possessing three hyperconjugated HC bonds), less in ethyl (containing two such bonds) and /so-propyl (one) and essentially
zero in ferf-butyl (n
o

hyperconjugated HC bond) group.

H

H
Methyl compound containing 3 HC hyperconjugated bonds

H
Hi
CH3
/jo-Propyl compound containing 1 HC hyperconjugated bond

It is important to note that although hyperconjugatioa like inductive effect causes the release of
electrons and thus the two effects reinforce each other in this respect, the magnitude of the two effects changes
in opposite direction in passing along a series of alkyl groups.
CH3f CH3.CH2, (CH^CHf (CH3)jC
Increasing inductive effect

Decreasing hyperconjugation

Theoretical Interpretation of hyperconjugation. The phenomenon of hyperconjugation may be

considered in terms of resonance as well as molecular orbital theory.
(i) Resonance: Hyperconjugation may be interpreted in terms of resonance. For example, propylene
may be regarded as the resonance hybrid between the following structures.
H

H+
H-C=CH-CH2
H

HC=CHCH<

*H

i
n
m
iv
Now since in resonating structures II to IV, there is no definite bond between one of the carbon atoms and
one of the hydrogen atoms, hyperconjugation is also known as no-bond resonance.
(ii)

Molecular orbital treatment: While considering the molecular orbital treatment of the process of hyperconjugation, it is presumed that the (CH bonding orbital) 5-orbital or the sp hybrid orbital

HC=CHCH
(du
e

or

H 2 C CH CH >

to some /^-character of the bonds)

overlaps to some extent with the /?orbitals on the adjacent carbon atoms to
form something like a non-localised k
-orbital. In other words, hyperconjugation
arises from the overlap of the CH
sigma bonding electrons of the alkyl
group with the ^-electrons of the double
bond.
Effects of hyperconjugation : Like
resonance, hyperconjugation is a device
used to interpret molecular properties in
terms of structural formulae. Since the
magnitude of the effect is much smaller
than that of resonance, hyperconjugation
can be regarded as a second-order
resonance. Hyperconjugation can affect
both physical and chemical properties of
molecules which is evident from the
following examples.

(/) Heat of hydrogenation : It is a

well known fact that for compounds of
similar structure, the smaller the heat of
hydrogenation or heat of combustion, the
more stable is the compound. The heat of
hydrogenation of ethylene and propylene
are 32.8 and 30.1 kcal/mole, respectively,
although the net change in both cases is
same.
> C=C < + H2
---------------- > CH-CH
<
The difference in the numerical values for
the heat of hydrogenation of ethylene and
propylene (32.8 - 30.1 = 2.7 kcal/gm
mole) indicates that propylene is more
stable than ethylene by 2.7 kcal/gm mole.
This extra stability can be attributed to
hyperconjugation Le. to the fact that
propylene is a resonance hybrid of the
following structures, whereas there is less

chance of resonance in the ethylene

molecule.
H

H* H H
i i _ i HCCH=CH2 H
C=CHCH2 <------------------------------------------>H + C=CH-CH2 <------------------------------------>
H*

H
(three
equivalent
forms)

Further substitution of the

hydrogen atoms of ethylene by methyl
groups
further
increases
the
hyperconjugation and thus lowers the heat
of hydrogenation. Thus in the case of
tetramethylethylene, there are more
possibilities of hyperconjugetion and
more (12) resonating forms with the result
its heat of

ii

H- C - H
CH 3 H

H * C -H
CH 3 H
i
i

i
i
i
HJC-CC--------C-H
-------------------H3C-C
-------------------C
-------------------C-H

i
i

H
Tetramethylethylene
(12 equivalent ionn%)
N
o
t
e
t
h
e
p
r
e
s
e
n

c
e
o
f
4
x
3
=
1
2
h
y
p
e

r
c
o
n
j
u
g
a
t
e
d
H
C
b
o
n

d
s

hydrogenation (26.6 kcal/gm mole) is still

lower and thus it is more stable than
ethylene by (32.8-26.6) 6.2 kcal/gm mole.
Thus
on
the
basis
of
hyperconjugation, we can explain greater
stability of the olefins in which the double
bond is centrally situated as compared
with the isomeric olefin having terminal
double bond. For example, 2-pentene is
more stable than 1-pentene by 2.3
kcal/mole.
H

H
H

CH3-C-CH=CH-CH
CH3-CH2-C-CH=CH2
I

I
I
H
H
H
2-Pentene
1-Pentene

Note the
presence
of 5 a C
H \
/Note
the

presence
of only 2
a C1
bonds
and
hence 6
resonati
ng
forms/
Ibonds
and
hence 3
resonati
ng
forms