 Reactions of Organic Compounds always involve the making and breaking of

covalent bonds.
 A Covalent Bond may break by two fundamentally different ways.

Heterolytic Cleavage of Bond

 In Heterolytic Cleavage of bond, there is an unequal distribution of electrons. One atom
gains both the electrons of the bond which makes the other atom lose them.
−

 This type of bond breaking is also called ionic cleavage.

 Positively charged carbon is called carbocation while the negatively charged carbon is called
carbanion.
 Homolytic Cleavage of Bond
 Bond cleavage in which equal distribution of electrons takes place during the chemical
reaction is known as Homolytic Cleavage.
 This type of cleavage of bond also known as Homolysis produces neutral, unpaired electron
species, known as free radicals.
 Homolytic Cleavage of Bond
 Bond cleavage in which equal distribution of electrons takes place during the chemical
reaction is known as Homolytic Cleavage.
 This type of cleavage of bond also known as Homolysis produces neutral, unpaired electron
species, known as free radicals.
 The effects which appear due to electronic displacement of covalently bonded
electrons are known as Electronic Effects or Electron Displacement Effects.

Electronic Effects

Temporary Effect Permanent Effect

Electromeric Effect Inductomeric Effect Inductive Effect Resonance Effect Hyperconjugation

 INDUCTIVE EFFECT
 Polarization of - bonded electrons either due to the electronegativity difference between
the atoms forming the bond or/and due to the electronegativity difference between the
atoms attached to these atoms when compared to atom.
 If an atom or group or ion pushes electrons away from itself when compared to atom then
it is said to be exhibiting + effect.
 If an atom or group or ion pulls electrons towards itself when compared to atom then it is
said to be exhibiting − effect.
 Lets check the inductive effect of − group.
 + -

  shows + effect
-
-

 Lets replace one of with another and then check.

 Increasing chain
increases + effect -
but the rate of
increase decreases.
 Lets replace one of with another and then one of with a .
-

 effect decreases
-
with distance.

 Lets replace the with a sp2 carbon.

+ -
=

  sp2 carbon has − effect. So does sp carbon.

 Inductive effect is a particle effect. This means it is the manifestation of the particle nature
of electrons.
 Inductive effect dissipates with distance.
 Inductive effect is a permanent effect.
 Inductive effect is a weak effect.
 Inductive effect is an ‘always’ effect.
 All negatively charged ions show + effect.
 Negatively charged ions have greater + effect than neutral atoms of groups.
 Among negatively charged ions + effect decreases with increase of electronegativity.
E.g. − − − − − − − −

 More the number of carbons in straight chain alkyl groups more is + effect.
 For the same number of carbons in two different alkyl groups + effect decreases with
distance.
 + effect increases with increase of mass of an isotope.

𝟏
Stretching frequency ∝
𝐌𝐚𝐬𝐬 𝐨𝐟 𝐈𝐬𝐨𝐭𝐨𝐩𝐞
Therefore, the stretching frequency is less for heavier isotopes which decreases the bond
length for heavier isotopes. This brings the electrons closer to carbon.
 + effect: − − − − − − − − − − − − − −
− −
 Groups with complete positive charge or partial positive charge or those with
electronegativity higher than show − effect.
 Groups with complete positive charge have greater − effect than those with partial positive
charge which have greater − effect than those without any charge.
 As ‘s-character’ of an atom increases its electronegativity increases which consequently
increases its − effect. E.g. −  − =
 − power: (sp) > (sp2) > (sp) > (sp3) > (sp2)
 − effect: − + − + − + − − −  − − − −
− − − − −  − − − =
 Why − + − + − + − + − − − + − + − +

 This order is only in solution phase where the solvent is polar.

 In aqueous solution, the of − + gets solvated or

hydrogen bonded with of water. Due to this

tends to give its electrons to while partially bonding
with . This decreases the positive charge of in
− +.
 Arrange the following atoms/groups/ions in the decreasing order of − effect:
(i) − − − (x) − − − −
(ii) − − − (xi) − + − +

(iii) − = − = − = (xii) −  + − = + − − +

(iv) − − − −

(v) −  −  −
(vi) − − − 

(vii) − + − + −
(viii) − − − − +
(ix) − − − −
(i) − − − (x) − − − −
(ii) − − − (xi) − + − +

(iii) − = − = − = (xii) −  + − = + − − +

(iv) − − − −

(v) −  −  −
(vi) − − − 

(vii) − + − + −
(viii) − − − − +
(ix) − − − −