CHE101 (B.Tech.

Chemistry Course)

Lecture - 24

Resonance and Hyperconjugation Effect

Edited By
Mr. Harminder Singh

Department of Chemistry Lovely Professional University, Phagwara, Punjab, India. E-mail: harminder.singh@lpu.co.in

Resonance

Resonance
Often a single Lewis structure does not accurately represent

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

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

Resonance
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 The real structure is a resonance hybrid or mixture of all three Lewis structures Double headed arrows are used to show that the three Lewis structures are resonance contributors to the true structure 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

Resonance
One resonance contributor is converted to another by the

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

A calculated electrostatic potential map of carbonate clearly

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

Resonance
Rules for Resonance:

Individual resonance structures exist only on paper The real molecule is a hybrid (average) of all contributing forms Resonance forms are indicated by the use of double-headed arrows Only electrons are allowed to move between resonance

structures
The position of nuclei must remain the same Only electrons in multiple bonds and nonbonding electrons can be

moved

Example: 3 is not a resonance form because an atom

has moved

Resonance
The energy of the actual molecule is lower than the energy

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

Unequal resonance structures contribute based on their

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

Resonance

Rules to Assign Relative Importance of Resonance

Forms
A resonance form with more covalent bonds is more

important than one with less Example: 6 is more stable and more important because it has more total covalent bonds

Resonance forms in which all atoms have a complete

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

Resonance
Resonance forms with separation of charge are less

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

Forms with negative charge on highly electronegative atoms

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

Resonance

Resonance

Example 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

Resonance theory can be used to produce three equivalent

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

Chapter 1

RESONANCE IN THE ACETATE ION

equivalent structures charge on oxygens

O
CH3 C

O CH3 C O H

-H+
base

O_

acetic acid

_
O
CH3 C O
acetate ion

_
O

PHENOLATE ION RESONANCE

O O

_ _ _
O

More structures, but not better than acetate.

_
Non-equivalent structures charge on carbon and oxygen

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.

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.

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

Resonance

+R or +M effect: a group is said to have +R or +M effect when the displacement of the electron pair is away from it. e.g. O-H, -O-R, -NH2 , -NHR, -X CH2 = CH NH2 (-) CH2 CH = NH2 (+)

-R or -M effect: a group is said to have R or M effect when the displacement of electron pair is towards it. e.g. NO2, >C=O, -CHO, -COOR, -CN CH2 = CH CH = O (+) CH2 - CH = CH O (-)

Hyperconjugation

In the study of the inductive effect, we have seen that an alkyl group has +I effect and relative order is (CH3)3C- > (CH3)2CH- > CH3- CH2- CH2- > CH3- CH2- > CH3- > -H But when alkyl group is attached to an unsaturated system, the above order get reversed.

Hyperconjugation: The spreading out of charge by the overlap of an empty p orbital with an adjacent 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

NO BOND RESONANCE

Hyperconjugation

Hyperconjugation
partial overlap of the 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 bond replacing a C-H bond with a C-C bond increases the possibility for hyperconjugation

Hyperconjugation

Application s of hyperconjugation 1. The order of carbocation stability is also a result of hyperconjugation. Example: CH3+ cannot be stabilized by hyperconjugation, but (CH3)2CH+ can.

Hyperconjugation
Hyperconjugation stabilizes the carbocation by donation of

electrons from an adjacent carbon-hydrogen or carboncarbon bond into the empty p orbital More substitution provides more opportunity for hyperconjugation

Or 1. relative stability of alkenes

2,3-Dimethylbut-2-ene > 2-methylbut-2-ene > but-2-ene > propene > ethene

2. Shortening of the carbon-carbon bond length adjacent to a multiple bond

e.g. propene

3. ortho and para directing nature of alkyl group in arenes e.g toulene