CHE101 (B.Tech.

Chemistry Course)

Lecture - 23

Basic of Electron Displacement Effect

Prepared By

Dr. ASHISH KUMAR

Department of Chemistry Lovely Professional University, Phagwara, Punjab, India. E-mail: ashishkr_dbdc@yahoomail.co.in

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Inductive effect

TYPES OF INDUCTIVE EFFECTS

ELECTRON WITHDRAWING GROUPS ELECTRON DONATING GROUPS

HCl

H C

H CH3

HC

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 groups that work through the T system.
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Inductive effect

y Inductive Effects
y Electronic effects that are transmitted through space and through the

bonds of a molecule y The effect gets weaker with increasing distance

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 Permanent displacement of electron along the chain of carbon atoms due to presence of atom or group of atom having different electronegativity at the end of the carbon chain. Electron withdrawing inductive effect or I effect -NO2 > -SO3H> -CN > -COOH > -F > -Cl > -Br > -I > OC6H5 > -COOR > -OR > - OH > -C6H5> -H  Electron donating inductive effect or +I effect -C(CH3)3 > -HC(CH3)2 > -C2H5 > -CH2CH3 > -CH3 > -H

Inductive effect

APPLICATION OF INDUCTIVE EFFECTS

H
Chlorine helps to stabilize -CO2by withdrawing electrons

 H

O O

Cl

C O

HCl

 H

H-

H+

H-

H+

C O

The effect diminishes with distance - it carries for about 3 bonds. Ashish Kumar 5 Prepared by:Dr.

 Influence on dipole moment

H-F = 1.90D H-Cl = 1.04D H-Br = 0.78D

 Comparison of relative acidic strength of alkynes

HC CH > CH3C CH > C2H5C CH

Inductive effect Factors that Determine Acid StrengthInductive Effects

When electron density is pulled away from the negative charge through W 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. The acidity of HA increases with the presence of electron withdrawing groups in A.

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Electromeric effect Electromeric 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 multibonded 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:

When the transfer of electrons takes place towards the attacking reagent, it is called + E (positive electromeric) effect. For example,

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 T and one W bond are converted to two W bonds

The T 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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Inductive effect

y The inductive effect

y the electron-deficient carbon bearing the positive charge

polarizes electrons of the adjacent sigma bonds toward it

y the positive charge on the cation is not localized on the

trivalent carbon, but delocalized over nearby atoms

y the larger the volume over which the positive charge is

delocalized, the greater the stability of the cation

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Inductive effect

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Resonance

y Resonance
y Often a single Lewis structure does not accurately represent the true

structure of a molecule y The real carbonate ion is not represented by any of the structures 1,2 or 3

y Experimentally carbonate is known not to have two carbon-oxygen single

bonds and one double bond; all bonds are equal in length and the charge is spread equally over all three oxygens

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Resonance
y The real carbonate ion can be represented by a drawing in which partial

double bonds to the oxygens are shown and partial negative charge exists on each oxygen y The real structure is a resonance hybrid or mixture of all three Lewis structures y Double headed arrows are used to show that the three Lewis structures are resonance contributors to the true structure y The use of equilibrium arrows is incorrect since the three structures do not equilibrate; the true structure is a hybrid (average) of all three Lewis structures

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Resonance
y One resonance contributor is converted to another by the use of curved

arrows which show the movement of electrons y The use of these arrows serves as a bookkeeping device to assure all structures differ only in position of electrons

y A calculated electrostatic potential map of carbonate clearly shows the

electron density is spread equally among the three oxygens y Areas which are red are more negatively charged; areas of blue have relatively less electron density

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Resonance
y Rules for Resonance:
y Individual resonance structures exist only on paper

The real molecule is a hybrid (average) of all contributing forms y Resonance forms are indicated by the use of double-headed arrows y Only electrons are allowed to move between resonance structures y The position of nuclei must remain the same y Only electrons in multiple bonds and nonbonding electrons can be moved y Example: 3 is not a resonance form because an atom has moved
y

y All structures must be proper Lewis structures

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Resonance
y The energy of the actual molecule is lower than the energy of any single

contributing form y The lowering of energy is called resonance stabilization y Equivalent resonance forms make equal contributions to the structure of the real molecule y Structures with equivalent resonance forms tend to be greatly stabilized y Example: The two resonance forms of benzene contribute equally and greatly stabilize it

y Unequal resonance structures contribute based on their relative stabilities

y

More stable resonance forms contribute more to the structure of the real molecule
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Resonance

y Rules to Assign Relative Importance of Resonance Forms y A resonance form with more covalent bonds is more important than one with less y Example: 6 is more stable and more important because it has more total covalent bonds

y Resonance forms in which all atoms have a complete valence shell of

electrons are more important y Example: 10 is more important because all atoms (except hydrogen) have complete octets

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Resonance
y Resonance forms with separation of charge are less important
y y

Separation of charge cost energy and results in a less stable resonance contributor Example: 12 is less important because it has charge separation

y Forms with negative charge on highly electronegative atoms are more

important y Those with positive charge on less electronegative atoms are also more important
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Resonance

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Resonance

y Example y The nitrate ion is known to have all three nitrogen-oxygen bond lengths the same and the negative charge spread over all three atoms equally

y Resonance theory can be used to produce three equivalent resonance

forms
Curved arrows show the movement of electrons between forms y When these forms are hybridized (averaged) the true structure of the nitrate ion is obtained
y

Chapter 1
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RESONANCE IN THE ACETATE ION

equivalent structures charge on oxygens

O C O_

O CH3 C O H

CH3 -H+
base

acetic acid

_
O CH3 C O
acetate ion
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_
O

PHENOLATE ION RESONANCE

O O

_ _ _
O O
More structures, but not better than acetate.

_
Non-equivalent structures charge on carbon and oxygen

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Resonance Factors that Determine Acid StrengthResonance Effects

Resonance is a factor that influences acidity. In the example below, when we compare the acidities of ethanol and acetic acid, we note that the latter is more acidic than the former.

When the conjugate bases of the two species are compared, it is evident that the conjugate base of acetic acid enjoys resonance stabilization, whereas that of ethanol does not.

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Resonance Resonance delocalization makes CH3COO more stable than CH3CH2O, so CH3COOH is a stronger acid than CH3CH2OH.

The acidity of HA increases when the conjugate base A: is resonance stabilized.

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Resonance Electrostatic potential plots of CH3CH2O and CH3COO below indicate that the negative charge is concentrated on a single O in CH3CH2O, but delocalized over both of the O atoms in CH3COO.C

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Hyperconjugation

Hyperconjugation: The spreading out of charge by the overlap of an empty p orbital with an adjacent W bond. This overlap (hyperconjugation) delocalizes the positive charge on the carbocation, spreading it over a larger volume, and this stabilizes the carbocation.

works for any sigma bond on the adjacent C secondary can do 2x, tertiary can do 3x
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Hyperconjugation

The order of carbocation stability is also a result of hyperconjugation. Example: CH3+ cannot be stabilized by hyperconjugation, but (CH3)2CH+ can.

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Hyperconjugation
y Hyperconjugation stabilizes the carbocation by donation of electrons from

an adjacent carbon-hydrogen or carbon-carbon W bond into the empty p orbital y More substitution provides more opportunity for hyperconjugation

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Hyperconjugation

y Hyperconjugation
y partial overlap of the W bonding orbital of an adjacent C-H bond with the

vacant 2p orbital of the cationic carbon delocalizes the positive charge and also the electrons of the adjacent W bond y replacing a C-H bond with a C-C bond increases the possibility for hyperconjugation

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Carbocation Cleavage of Covalent Bonds

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Carbocation

Radicals and carbocations are electrophiles because they contain an electron deficient carbon. Carbanions are nucleophiles because they contain a carbon with a lone pair.

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Carbocation

Structure of carbocation:

Carbocations are classified as primary (1o), secondary (2o), or tertiary (3o), based on the number of R groups bonded to the charged carbon atom. As the number of R groups increases, carbocation stability increases.

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Carbocation

More positive charge at C+ = a more unstable C+

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Carbocation

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Carbocation

Carbocation Stability
The order of carbocation stability is also a consequence of

hyperconjugation. Hyperconjugation is the spreading out of charge by the overlap of an empty p orbital with an adjacent W bond. This overlap (hyperconjugation) delocalizes the positive charge on the carbocation, spreading it over a large volume, and this stabilizes the carbocation. Example: CH3+ cannot be stabilized by hyperconjugation, but (CH3)2CH+ can.

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Free radicals

y Free Radicals:
y Homolytic bond cleavage leads to the formation of radicals (also called

free radicals) y Radicals are highly reactive, short-lived species y Single-barbed arrows are used to show the movement of single electrons

y Production of Radicals y Homolysis of relatively weak bonds such as O-O or X-X bonds can occur with addition of energy in the form of heat or light
o or

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Free radicals Homolytic Bond Dissociation Energies and the Relative Stabilities of Radicals: The formation of different radicals from the same starting compound offers a way to estimate relative radical stabilities Examples: The propyl radical is less stable than the isopropyl radical

\ Likewise the tert-butyl radical is more stable than the isobutyl radical

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Free radicals The relative stabilities of radicals follows the same trend as for carbocations The most substituted radical is most stable Radicals are electron deficient, as are carbocations, and are therefore also stabilized by hyperconjugation

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Free radicals
Example of free radical Reaction:Chlorination of Methane: Mechanism of Reaction The reaction mechanism has three distinct aspects: Chain initiation, chain propagation and chain termination

Mechanism:

Chain termination

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Free radicals 2.Radical Addition to Alkenes: The anti-Markovnikov Addition of Hydrogen Bromide in presence of peroxide:

Mechanism:

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Free radicals

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Carbocation stability Carbocations are classified as primary (1o), secondary (2o), or tertiary (3o), based on the number of R groups bonded to the charged carbon atom. As the number of R groups increases, carbocation stability increases.

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Carbocation stability

y Carbocation Stability

y The inductive effect

y the electron-deficient carbon bearing the positive charge

polarizes electrons of the adjacent sigma bonds toward it

y the positive charge on the cation is not localized on the

trivalent carbon, but delocalized over nearby atoms

y the larger the volume over which the positive charge is

delocalized, the greater the stability of the cation

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Carbocation stability

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Carbocation stability

Carbocation Stability
The order of carbocation stability is also a consequence of

hyperconjugation.

Hyperconjugation partial overlap of the W bonding orbital of an adjacent C-H bond with the vacant 2p orbital of the cationic carbon delocalizes the positive charge and also the electrons of the adjacent W bond replacing a C-H bond with a C-C bond increases the possibility for hyperconjugation

Example: CH3+ cannot be stabilized by hyperconjugation, but (CH3)2CH+

can.

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Carbocation stability

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Carbanion stability

y Carbanions have 8 valence electrons and a negative charge

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Carbanion stability

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Carbanion stability

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Carbanion stability

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Carbanion stability

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Carbanion stability

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Carbanion stability

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Carbanion stability

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Kinds of Organic Reactions

Types of Organic Reactions:

A substitution is a reaction in which an atom or a group of atoms is replaced by another atom or group of atoms. In a general substitution, Y replaces Z on a carbon atom.

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Kinds of Organic Reactions

Substitution reactions involve W bonds: one W bond breaks and another forms at the same carbon atom. The most common examples of substitution occur when Z is a hydrogen or a heteroatom that is more electronegative than carbon.

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Kinds of Organic Reactions

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Kinds of Organic Reactions Elimination is a reaction in which elements of the starting material are lost and a T bond is formed.

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Kinds of Organic Reactions

In an elimination reaction, two groups X and Y are removed from a starting material. Two W bonds are broken, and a T bond is formed between adjacent atoms. The most common examples of elimination occur when X = H and Y is a heteroatom more electronegative than carbon.

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Kinds of Organic Reactions

Addition is a reaction in which elements are added to the starting material.

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Kinds of Organic Reactions In an addition reaction, new groups X and Y are added to the starting material. A T bond is broken and two W bonds are formed.

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Kinds of Organic Reactions Addition and elimination reactions are exactly opposite. A T bond is formed in elimination reactions, whereas a T bond is broken in addition reactions.

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Kinds of Organic Reactions Classify each of the following as either substitution, elimination or addition reactions. a)
r

b)

c)

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Kinds of Organic Reactions

Some other examples:

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