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Lecture - 23
E-mail: harminder.singh@lpu.co.in
The inductive effect arises in the organic molecules when some atom or group of different electronegativity is attached to the carbon atom chain.
dX
d+ C
d+ Y
dC
X is more electronegative
Y is less electronegative
As a result, the electron pairs of the chain get displaced either towards it if it is more electronegative then carbon or away from it in case it is less electronegative. the electron displacement will lead to polarity( i.e. partial + and ve charge)
The permanent displacement of the electrons along the chain of carbon atoms due to the presence of an atom or group of different electronegativity at the end of the chain is called Inductive effect.
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Inductive effect
dCl
d+ C
d+
CH3
dC
F, Cl, Br, N, O
R, CH3, B, Si
electronegative elements alkyl groups and elements take electron density less electronegative than carbon from cabon donate electron density to carbon These electron withdrawing and donating groups work through the sigma bond system, unlike the similarly named resonance
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-I effect - NO2 > -SO3H > -CN > -COOH > -F > -Cl > -Br > -I > -OCH3 > -C6H5 > -H +I effect
(CH3)3C- > (CH3)2CH- > CH3- CH2- CH2- > CH3- CH2- > CH3- > -H
Inductive effect
d- d+ C Cl O C O
O O
d-
d+
d-
d+
d-
d+
Cl
Inductive effect
Inductive Effects
Electronic effects that are transmitted through space and
through the bonds of a molecule The effect gets weaker with increasing distance
Inductive effect
The
inductive effect
Inductive effect
When electron density is pulled away from the negative charge through bonds by very electronegative atoms, it is referred to as an electron withdrawing inductive effect. More electronegative atoms stabilize regions of high electron density by an electron withdrawing inductive effect. The more electronegative the atom and the closer it is to the site of the negative charge, the greater the effect.
This is a temporary effect and takes place between two atoms joined by a multiple bond, i.e., a double or triple bond. It occurs at the requirements of the attacking reagent, and involves instantaneous transfer of a shared pair of electrons of the multiple bond to one of the linked atoms. It is temporary in nature because the molecule acquires its original electronic condition upon removal of the attacking reagent.
For example, consider the carbonyl group, >C=O, present in aldehydes and ketones. When a negatively charged reagent say approaches the molecule seeking positive site, it causes instantaneous shift of electron pair of carbonyl group to oxygen (more electronegative than carbon). The carbon thus becomes deprived of its share in this transferred-pair of electrons and acquires positive charge. In the meanwhile oxygen takes complete control of the electron pair and becomes negatively charged. Therefore, in the presence of attacking reagent, one bond is lost and this negatively charged attacking reagent links to the carbon having positive charge.
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Electromeric effect
This phenomenon of movement of electrons from one atom to another at the demand of attacking reagent in multi-bonded atoms is called electromeric effect, denoted as E effect. The electromeric shift of electrons takes place only at the moment of reaction. Like the inductive effect, the electromeric effect is also classified as +E and E:
+E- effect
When the transfer of electrons takes place towards the attacking reagent, it is called + E (positive electromeric) effect. For example,
+E- effect
When the transfer of electrons takes place away from the attacking reagent, it is called, -E (negative electromeric) effect. For example,
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Electromeric effect
Ex.of application of electromeric effect: Additions to Alkenes
Generally the reaction is exothermic because one p and one bond are converted to two bonds
The p electrons of the double bond are loosely held and are a source of electron density, i.e. they are nucleophilic Alkenes react with electrophiles such as H+ from a hydrogen halide to form a carbocation
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