Q: Discuss in detail inductive effect.
10 marks
Inductive Effect
Definition:
The polarization of one bond caused by the polarization of an adjacent bond is
called
inductive effect. OR The permanent dipole induced in one bond by another through
movement of σ electrons, is called inductive effect.
Principle
The hydrocarbons contain carbon and hydrogen atoms and are thus non-polar in
nature as there is not much difference in the electronegativity of carbon and
hydrogen. For example, in alkanes carbon—carbon and carbon—hydrogen σ
bonds are present. If we replace the hydrogen by some other atom which differs
appreciably in its electronegativity compared to carbon, then it results in the
induction of polarity in the molecule. If we replace hydrogen by an atom like
fluorine, which is more electronegative than carbon, fluorine will carry a partial
negative charge(ᵟ -) , as it will attract shared electrons towards itself and thus,
the carbon skeleton will carry partial positive charge. This carbon, in turn,
induces a small positive charge(ᵟ +) on the adjacent carbon. Similarly, when
hydrogen is replaced by an atom such as lithium which is more electropositive
than carbon, the lithium will carry a partial positive charge(ᵟ +) . Now, carbon
being more electronegative attracts the shared electrons towards itself and will
carry a partial negative charge(ᵟ -) . This induces a small negative charge on
adjacent carbon atom. This induction of polarity in a bond through another bond
is termed as inductive effect.
Charateristics of inductive effect:
It is represented by ‘’I’’ symbol.
It is a permanent effect.
This effect operates through σ bonds.
It is observed for a maximum of upto second carbon atom of the chain and
ceases to operate beyond fourth carbon.
As the attachment of the number of groups, exhibiting either +I or —I effect,
on a carbon increases it experiences the corresponding inductive effect to a
greater extent.
Types of inductive effect
i) -I inductive effect
The atoms or groups which are more electronegative than carbon, withdraw
electrons from carbon and are said to exhibit -I effect (minus I effect). –I effect
increases with the increase in the number of electronegative atom/groups. –I
effect also increases with the increase in the power of an atom or group to
withdraw shared pair of electrons(highly electronegative atom) e.g F has more
–I effect as compared to Cl.
Examples of substituents having –I effect:
Increasing order of –I effect of the substituents is given below:
ii. +I inductive effect
The atoms or groups which are more electropositive (less electronegative)
as compared to carbon, release electrons towards carbon and are said to
exhibit +I effect (plus I effect). +I effect increases with the increase in the
number of alkyl groups. E.g tertiary alkyl group has more +I effect than
secondary alkyl group, which has more +I effect than primary alkyl group.
Methyl group has lowest +I effect, while ‘H’ has negligible effect.
Examples of substituents having +I effect:
Increasing order of +I effect of the substituents is given below:
Applications of inductive effect on properties of organic compounds
Being a permanent effect, the inductive effect affects the physical and chemical
properties of molecules. Some of these like reactivity of alkyl groups, decrease in
bond lengths, origin of dipole moments, strength of acids and bases, are
considered as applications of inductive effect.
1) Reactivity of Alkyl Halides:
The presence of halogen atoms in the molecule of an alkyl halides creates a
centre of low electron density (electrophilic centre) on the adjacent carbon which
is readily
attacked by the negatively charged reagents (Nucleophiles). So, reactivity of alkyl
halides towards nucleophiles is due to –I effect of halogens.
eElectrophilic
8+ 8-
CH3—Cl
2) Effect on Bond Lengths. The bond length decreases with increase in inductive
effect( either +I or –I), because the covalent bond assumes increased ionic
character with the increase in the electronegativity difference (increase in
inductive effect). E.g
Due to increase in the radius and decrease in electronegativity of halogen from
F to I, inductive effect decreases and bond length increases
The bond length of C—F, C—C1, C—Br and strength of inductive effect are in the
order given below.
C—F < C—C1 < C—Br < C—I
increase in inductive effect and decrease in bond length
3) Dipole Moment: A covalent bond acquires a dipolar character because of the
inductive effect (either +I or –I), resulting in the dipole moment( a product of
the concentration of charges on the atoms and the distance between the
atoms) which is an important physical property used in structure elucidation. As
the inductive effect ( either +I or –I), increases, dipole moment also increases
due creation of charges on atoms.
H3C > I H3C > Br H3C—>—CI
increase in -I inductive effect and increase in dipole
4) Strength of Aliphatic Acids(aliphatic carboxylic acids): The difference in the
strength of various aliphatic acids may be explained on the basis of inductive
effect.
KEY POINTS TO MEMBER:
Acidity may be defined as an ability to donate hydrogen ion.
Thus acidic strength increases as the ability of an acid to donate proton
increases
( if it donates proton easily or readily it is strong acid).
The acidic strength increases with increase in the stability of conjugate base
of that acid after removal of the proton i.e greater the stability of a conjugate
base (carboxylate ion) , higher will be the acidic strength or in other words the
more destabilized the conjugate base (carboxylate ion) the less acidic the
acid will be.
+I groups/atom destabilizes the conjugate base so decreases the acidic
strength ascompared to –I groups/atom that stabilizes the conjugate base
(carboxylate ion) andincreases the acidic strength of aliphatic carboxylic
acids.
Greater the –I effect of substituents, greater will be the acidic strength.
a. Affect of +I effect on acidic strength:
With increase in +1 effect, removal of hydrogen as proton becomes more
difficult thus there will be decreases in the acid strength. More the +I
effect more will be destabilization of conjugate base (carboxylate ion)
thus acidic strength decreases with increase in +I inductive effect.
Example:
Acidic strength decreases from formic acid to butyric acid as conjugate base
(carboxylate ion) of butyric acid is less stable than formic acid. This is because
the +1 effect of alkyl groups increases in the order H<-CH3<-C2H5<-C3H7.
Formic acid>acetic acid>propionic acid> butyric acid
Acidic strength decreases with increase in +I effect
b. Affect of -I effect on acidic strength:
If the halogens are substituted in alkyl group, then because of -I effect
due to halogens the strength of halogen substituted acids will increase
with increase in the -I effect of halogen or number of halogens attached
to the alkyl group. Greater the –I effect greater will be the stabilization of
the conjugate base (carboxylate ion) and greater will be the acidic
strength.
Example:
The strength of the acetic acid has been compared with the halogen substituted
acids in the data given below:
Trichloroacetic acid> dichloroacetic acid>chloroacetic acid>bromoacetic acid>acetic
acid
Acidic strength increases with increase in –I inductive effect
5) Affect on basic strength of aliphatic bases (aliphatic amines)
The difference in the base strength of various amines may be explained
conveniently on the basis of inductive effect.
KEYPOINTS TO MEMBER:
Basic strength may be defined as a measure of the capacity to donate an
electron pair for sharing or ability to accept proton(hydrogen ion).
Greater the +I effect greater will be the basic strength of the amines i.e
the amines substituted with +I substituents have ability to donate electron
pair more readily/fastly than the ammonia.
The amines, substituted with –I atom/groups are less basic than
ammonia and other aliphatic amines which are substituted with +I
atom/groups because the –I substituents withdraw lone pair of nitrogen
towards them thus, make it less available for donation to proton and
decreases the basic strength.
+I substituents(alkyl groups) increases the basic strength of aliphatic
amines due to their ability to donate shared pair of electrons to the nitrogen
thus, making the lone pair more available to incoming the proton.
-I substituents decreases the basic strength of aliphatic amines by
withdrawing electron pair from nitrogen thus, making it less available to
accept the proton.
Example: The strength of the ammonia has been compared with the
substituted amines in the data given below:
trimethylamine>dimethylamine>methylamine>ammonia
Basicity increases as +I effect increases
Other factors affecting basicity of amines:
Inductive effect alone does not determine the basic nature, pkb of trimethyl
amine is 4.22. The decrease in its basic character is due to the steric effect (the
obstruction or crowding caused by the bulky / large size of substituent groups
attached to electron donating atom (N or O) in a molecule) of three methyl
groups that surround the lone pair of nitrogen thus, make it less available for
donation to proton. Comparative strength of a few bases according to steric
effect and pkb values is given below:
Dimethylamine <methylamine <trimethylamine< ammonia
pkb values increases( basic strength decreases) as steric effect increases