Essential Organic Chemistry

Paula Yurkanis Bruice

Chapter 7

Delocalized Electrons and Their Effect

on Stability, Reactivity, and pKa
Localized Electrons vs. Delocalized Electrons
 Localized electrons:
Electrons that are restricted to a particular region.

 “Delocalized” electrons:
Neither belong to a single atom nor are confined to a
bond between two atoms, but are shared by three or
more atoms.
 7.1 The Structure of Benzene

The Lewis representation of benzene suggests that we

deal with a six-membered ring of carbon atoms that
are held together by alternating single and double
bonds.
H
H C: 6 • 4 = 24 valence electrons
H H: 6 • 1 = 6 valence electrons
----------------------------------------
Total = 30 electrons
H H = 15 bonds
H
 Benzene
This implies that we should observe alternating
short (1.33 Å) and long (1.54 Å) bond lengths.

Modern analytical techniques showed that all bond

lengths are the same (1.39 Å). Thus, they must have
the same number of electrons between the carbon
atoms, this can be so only if the π electrons are
delocalized around the ring.
 Benzene

Since both representations are equal, in average

each
C-C bond has a bond character in between a single
and a double bond.
Measured bond length is: 1.39 Å
 Benzene
H
This also explains why H H 2x X

replacing two of the six

H H
hydrogens produces only H
three isomers. In case of X X X

alternating double and H X H H H H

single bonds, A and B H H H X H H

should be different and we H
A
H X
X
should have four isomers.
X X X
H X H H H H

H H X H H H
H B H X
 7.2 Benzene Has Delocalized Electrons

a. C-C and C-H sigma bonds in benzene

b. Benzene is planar and six p orbitals are parallel. P orbitals
are close enough for side-to-side overlap.
c. Overlapping p orbitals form a doughnut-shaped cloud of
electrons above and below the benzene ring.
d. All C-C bonds have the same electron density.
7.3 Resonance Contributors and Resonance Hybrid

• When it is possible to draw more than one valid Lewis

diagram for a molecule or ion, that species is said to
have resonance (electrons are delocalized).
• The molecule or ion is said to be a resonance hybrid
of the structures drawn.
• For species with resonance, no single Lewis diagram
will suffice to describe them correctly.
• Dashed lines inside benzene do not show how many π
electrons are in the ring.
Resonance Contributors and Resonance Hybrid
• Chemists prefer to use approximate structures.
• The approximate structure with localized electrons is
called a resonance contributor.
• The actual structure with delocalized electrons is called
a resonance hybrid.
Resonance Contributors and Resonance Hybrid

• Electron delocalization occurs only if all the atoms

sharing the delocalized electrons lie in or close to the
same plane, so that their p orbitals can effectively
overlap.
 7.4 How to Draw Resonance
Contributors
 Delocalized electrons result from a p orbital
overlapping the p orbitals of more than one adjacent
atom.
Rules for Drawing Resonance Contributors

• Only electrons move. The nuclei of the atoms

never move.
• The only electrons that move are  electrons or
lone-pair electrons.
• The total number of electrons in the molecule
doesn’t change. All resonance contributors have
the same net charge.
Rules for Drawing Resonance Contributors

• Electrons are always moved toward an sp2 carbon.

• An sp2 carbon is either a positively charged
carbon or a double-bonded carbon.

• Electrons cannot be moved toward an sp3 carbon,

because an sp3 carbon cannot accept any more
electrons, it has a complete octet.
Rules for Drawing Resonance Contributors

• Moving lone-pair
electrons toward an sp2
carbon.
• The sp2 carbon can
accommodate the new
electrons by breaking a π
bond.
 Resonance

We move only the electrons

N N N
CH3 CH3 CH3

All atoms are sp2 hybridized

7.5 Predicted Stabilities of Resonance Contributors

 All resonance contributors do not necessarily contribute

equally to the resonance hybrid.
 The greater the predicted stability of the resonance
contributor, the more it contributes to the structure of
resonance hybrid, and the more similar the contributor
is to the real molecule.
Predicted Stabilities of Resonance Contributors

 Structure B is less stable than A because:

1. One of its oxygen has a positive charge.
2. It has “separated charges” (it takes energy).
Predicted Stabilities of Resonance Contributors

 Structures C and D are equally stable.

7.6 Delocaliztion Energy is The Additional Stability
Delocalized Electrons Give to a Compound
 Delocalized electrons
stabilize a compound.
 The extra ability gains
from having delocalized
electrons is called
resonance stabilization or
resonance energy.
 The greater the number of
relatively stable resonance
contributor and the more
nearly equivalent they are,
the greater is the
resonance stabilization.
7.7 The Effect of Delocalized Electrons on Stablility
 Dienes are hydrocarbons with two double bonds.
 Conjugated dienes have conjugated double bonds, each separated
by one single bond.
 Isolated double bonds are separated by more than one single bond.

 π Electrons in an isolated diene are localized, while π electrons

in a conjugated diene are delocalized.
 Conjugated dienes are more stable than isolated dienes.
The Effect of Delocalized Electrons on Stablility

 Because allylic cation and benzylic cation have delocalized

electrons, they are more stable than other primary carbocations.
The Effect of Delocalized Electrons on Stablility

 Not all allylic and benzylic carbocations have the same stability.
 7.8 The Effect of Delocalized Electrons on the
Nature of the Product Formed in a Reaction

 The reactions of isolated dienes are like the reactions of alkenes.

The Effect of Delocalized Electrons on the Nature
of the Product Formed in a Reaction
 When a conjugated diene reacts with a limited amount of HX,
only two addition products are formed:
One is a 1,2-addition product, the other is a 1,4-addition product.
7.9 The Effect of Delocalized Electrons on pKa

 An increase in resonance stabilization means an

increase in stability.
 Loss of proton from a carboxylic acid is accompanied
by an increase in resonance stabilization.
The Effect of Delocalized Electrons on pKa- Phenol
The Effect of Delocalized Electrons on pKa- Aniline
The Effect of Delocalized Electrons on pKa