Organic Chemistry

Global Edition
David Klein

Chapter 2
Molecular Representations

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
 2.1 Representing Molecules
• There are many ways to represent molecules

• Consider what information is necessary to accurately

describe a molecule.
• Which representations are easiest to draw? Which
ones give you more information about the molecule?

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
 2.1 Representing Molecules

• Notice that the molecular formula would be inadequate to

distinguish between propanol and isopropanol.

• Practice converting from one type of representation to

another with Skillbuilder 2.1
Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
 2.2 Bond-Line Structures
• Lewis structures are too impractical to represent a
compound like Amoxicillin, because of it’s size. But
condensed formulas would tell very little about it’s
shape.

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
 2.1 Representing Molecules

Lewis
structure

• The Bond-line structure (also called a skeletal structure) is

easier to read and to draw

bond-line
structure

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
 2.1 Representing Molecules
• Bond-line structures are the benchmark representations for
organic compounds
• It is critical to known how to draw these structures, for any
compound, without difficulty, to succeed in any organic
chemistry course.

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
 2.2 How to Read Bond-Line Structures
• Each corner or endpoint represents a carbon atom. There are
six carbon atoms in hexane and four in 2-butene and 2-butyne:
4
2 4 6 1 3 3
2
1 5 4
3 2
1

• The zigzag format is fairly accurate in representing the bond

angles for sp3 and sp2 hybridized atoms
– Linear geometry is shown for sp-hybridized atoms?
• Carbon atoms are not labeled, but a carbon is assumed to be
located at every corner or endpoint on the zigzag.
• H atoms bonded to carbon are not drawn

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
 2.2 How to Read Bond-Line Structures
• You must also be able to use the bond-line structure language
to interpret the number and location of H atoms in a molecule

• H atoms are not shown, but its assumed there are enough to
complete the octet (4 bonds) for each carbon

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
 2.2 How to Read Bond-Line Structures
• Practice identifying the location of carbons and hydrogens in a
skeletal structure. In your mind’s eye you should see the
hydrogens and where they are located.

• Practice with Skillbuilder 2.2

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
 2.2 How to Draw Bond-Line Structures
• If you are given a Lewis structure or condensed structure, you
must also be able to draw the corresponding bond-line
structure

Rule 1: sp2 and sp 3 hybridized atoms in a straight chain should

be drawn in zigzag format

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
 2.2 How to Draw Bond-Line Structures
Rule 2: When drawing double bonds, draw all bonds as far apart as
possible

Rule 3: When drawing single bonds, the direction in which the

bonds are drawn is irrelevant

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
 2.2 How to Draw Bond-Line Structures
Rule 4: All heteroatoms (other than carbon and hydrogen) must be
drawn, as well as the H atoms attached to them.

Rule 5: The cardinal rule – Never draw more than four bonds to a
carbon atom (recall the octet rule).

Practice with Skillbuilder 2.3

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
 2.2 Identifying Functional Groups
• Bond-line structures make it easier to see the bonds
made/broken in a chemical reaction
• Compare the condensed formula with the bond-line structure
below for the same reaction

• The bond-line structures make it more obvious to see the

functional group transformation that takes place

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
 2.2 Identifying Functional Groups
• When certain atoms are bonded together in specific
arrangements, they undergo specific chemical reactions

• These characteristic groups of atoms/bonds are called

functional groups. Every chemistry student needs to learn the
term for each functional group (Table 2.1)

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
 2.2 Identifying Functional Groups

• Practice with conceptual checkpoint 2.7

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
 2.3 Carbon Atoms with Formal Charges
• A carbon atom will have 4 bonds when it does not have a formal
charge
• When a carbon has a positive charge (carbocation), it will have a
total of three bonds (and one empty orbital).

• A carbanion will also have

three bonds, but also a lone pair.
(no empty orbitals)

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
2.3 Carbon Atoms with Formal Charges
• Formal charge (section 1.4) affects the stability and reactivity of
molecules, so you must be able to identify formal charges in
bond-line representations
• The following structure is incomplete, because it doesn’t have
formal charges correctly indicated.

• Formal charges must always

drawn. Fix the structure by
adding them

• Practice with conceptual checkpoints

2.12 and 2.13

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
 2.5 Bond-line structures: Identifying Lone
Pairs
• Formal charge must be drawn, always, but drawing lone pairs is
optional and they are often not included.
• By knowing the formal charge, the presence (or absence) of lone
pairs is implied

• Oxygen is in 6th group of PTE, needs 6 valence electrons to be

neutral, so an oxygen anion has 7. The negatively charged oxygen
has one bond, so it must have 6 unshared electrons to total 7.

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
 2.5 Bond-line structures: Identifying Lone
Pairs
• Oxygen has three possible bonding patterns (the same three
patterns for any 2nd-row atom with 5, 6 or 7 valence electrons

when O has 7 when O has 6 when O has 5

valence e- valence e- valence e-

• Practice with SkillBuilder 2.4

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
 2.5 Bond-line structures: Identifying Lone
Pairs
• The formal charge on a N atoms can be calculated the same way
or by matching its bonding pattern with its formal charge

When N has 6 When N has 5 When N has 4

valence e- valence e- valence e-

• Practice with SkillBuilder 2.5

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
 2.6 Bond-line Structures in 3-D
• All molecules take up spaced in 3 dimensions, but it is difficult to
represent a 3D molecule on a 2D piece of paper or blackboard

• We will use dashed and solid wedges to show groups that point
back into the paper or out of the paper

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
 2.6 Bond-line Structures in 3-D
• Other ways to show 3-D structure

• The shape of a compound governs how it interacts biologically,

and so it is important to accurately depict and interpret 3-D in
bond-line structures.
Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
 2.7 – Introduction to Resonance
• Pi-bonds and/or formal charges are often more “spread out” than
a bond-line structure can imply

• Consider the allyl carbocation. In this case, the pi-bond and the
positive are inadequately described by a bond-line structure.

There is a p-orbital on
2 carbon 1, 2 and 3…
1 3

… so the pi-bond is also delocalized

between carbons 2 and 3

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
 2.7 – Introduction to Resonance
• If all of the carbons have unhybridized p orbitals, then all 3 of
them overlap side-on-side, and

• All three overlapping p orbitals allow the electrons to move

throughout the overlapping area, and so we say the molecule has
resonance (meaning it has delocalized electrons).

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
 2.7 – Introduction to Resonance
• From a molecular orbital point
of view, the THREE unhybridized
p-orbitals overlap to form
THREE new MOs

• The two pi-electrons occupy the

lowest energy MO, which is the
bonding MO

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
 2.7 – Introduction to Resonance
• The allyl carbocation has a
charge of +1. If it gained an
electron it would go to the non-
bonding MO

• The symmetry of the non

bonding MO suggests the
cationic charge is spread out to
both ends of the 3 carbon chain
(not just one carbon atom drawn
with the positive charge)

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
 2.7 Resonance
• So how can we use bond-line structures accurately describe the
positive charge on the allyl carbocation?

• The pi electrons can exist on both sides of the middle carbon, so

we can draw two different resonance structures to represent the
compound

• The resonance arrow, and the brackets, indicate these structures

are describing one compound
Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
 2.7 Resonance
• Because neither of the contributors exists (look at MOs), the
average or hybrid is much more appropriate

vs.
δ+ δ+

Two resonance contributors one resonance hybrid

The resonance structures are not switching back and forth!

• Analogy: a nectarine is a hybrid formed by mixing a peach and a
plum. A nectarine is does not switch back and forth between
being a peach and a plum. It is simply a nectarine, all of the time

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
 2.7 Resonance
• Delocalized electrons are more spread out, thus lower energy,
thus more stable. So resonance stabilizes a molecule
– Electrons exist in orbitals that span a greater distance giving
the electrons more freedom minimizing repulsions
– Electrons spend time close to multiple nuclei all at once
maximizing attractions

• Delocalization of charge
– The charge is spread out over more than one atom. The
resulting partial charges are more stable than a full +1 charge.

δ+ δ+
Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
.8 Curved Arrows
2.8 Curved Arrows
this section, we will focus on curved arrows, which are the tools nec
• Throughout Organic Chemistry, we will be using curved arrows to
uctures properly. Every curved arrow has a tail and head:
show electron movement
Tail Head

urved arrows used for drawing resonance structures do not represent the m
• The sooner you master this skill, the easier the course will be
e simply tools that allow us to draw resonance structures with ease. These
– The arrow starts where the electrons are currently located
hey were moving, even though the electrons are actually not moving at
– The arrow ends where the electrons will end up after the
counter curved arrows that actually do represent the flow of electrons. Fo
electron movement
curved arrows in this chapter are just tools and do not represent a flow o
It is essential that the tail and head of every arrow be drawn in prec
e tail shows where the electrons are coming from, and the head show
ing (remember, the electrons aren’t really going anywhere, but we treat
• We will
e purpose of explore
drawingcurved arrows tostructures).
the resonance show other We
reactions in Chapter
will soon learn pat
3
rved arrows. But, first, we must learn where not to draw curved arrows
ust be followed when drawing curved arrows for resonanceKlein, Organicstructures:
Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Chemistry GE
 2.8 Curved Arrows
• There specific rules for using curved arrows to describe electron
delocalization (i.e. resonance)

Rule 1: Never show a single (sigma) bond as being delocalized

• Single bonds break in a chemical reaction, not resonance.

• Resonance occurs for electrons existing in overlapping p orbitals
(pi-bonds and lone pairs… not sigma bonds)

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
 2.8 Curved Arrows
Rule 2: Never exceed an octet for 2nd row elements (B, C, N, O, F)

• The valence shell of an atom in the 2nd row has only 4 orbitals,
holding a max. of 8 electrons

• These curved arrows violate rule 2.

Bad arrow

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
 2.8 Curved Arrows
• 2nd row elements (B, C, N, O, F) will sometimes have LESS than an
octet, just never more than an octet.

• Practice with SkillBuilder 2.6

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
 2.9 Formal Charges in Resonance
• When using curved arrows to derive resonance structures, you
will often have one or more formal charges to contend with.

• You have to be able to indicate formal charge to draw a valid

structure.

• Consider the resonance structure derived from the curved arrows

shown below:

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
 2.9 Formal Charges in Resonance
• We can draw the other resonance structure by following the
instructions provided by the curved arrows…

… but we have to show the formal charges to draw it correctly:

• Do Skillbuilder 2.7 and Practice the Skill 2.15 and 2.16

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
 2.10 Resonance Pattern Recognition
• There are 5 general bonding patterns in which resonance occurs.
Recognize these patterns to predict when resonance will occur

1. Allylic lone pair

2. Allylic carbocation
3. Lone pair of electrons adjacent to a carbocation
4. A pi bond between two atoms with different
electronegativities
5. Conjugated pi bonds in a ring

• The only way to recognize these patterns is to do lots, and lots of

practice problems and examples.

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
2.10 Resonance Pattern Recognition
• Vinyl and allyl refer to the atoms of the pi bond and next door to
the C=C double bond, respectively

• We look for allylic lone pairs because they will be resonance

delocalized

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
2.10 Resonance Pattern Recognition
• All of the lone pairs drawn in these examples are allylic

• Two curved arrows must be used to show the delocalization of an

allylic lone pair.

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
2.10 Resonance Pattern Recognition
• When the atom with the allylic lone pair has a negative charge,
the charge is delocalized with the lone pair, shown here.

• If the allylic atom is neutral, then it will become positive, and the
atom receiving the lone pair will become negative.

• Practice with Conceptual Checkpoint 2.18

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
2.10 Resonance Pattern Recognition
2. Allylic carbocations

Only one curved arrow is needed

to show resonance

• If there are multiple double bonds (conjugated), then multiple

contributors are possible. They are drawn by moving one
electron pair at a time

A total of three resonance structure for this allylic carbocation

Practice with Conceptual Checkpoint 2.19

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
2.10 Resonance Pattern Recognition
3. A lone pair adjacent to a carbocation
• Only one arrow is needed

• Recognize how the formal charges are affected by the electron

movement in these two examples

Practice with Conceptual Checkpoint 2.20

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
2.10 Resonance Pattern Recognition
4. A pi bond between atoms of different electronegativity
• The pi electrons will be more attracted to the more
electronegative atom, causing the pi bond to be unequally shared

• These two structure represent the “extreme” descriptions of the

pi-bonded electrons (equally shared versus not shared). The
actual compound is a hybrid of the two (unequally shared).

• Practice with conceptual checkpoints 2.21-2.23

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
2.10 Resonance Pattern Recognition
5. Conjugated pi bonds in a ring
• Each atom in the ring has an unhybridized p orbital that can
overlap with its neighbors

• The pi bonds can be pushed over by one position (clockwise or

counterclockwise, doesn’t matter, the result is the same).

• Practice with conceptual checkpoint 2.24

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
 2.10 Resonance Pattern Recognition
Summary of the 5 main patterns

Practice with conceptual checkpoint 2.25

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
 2.10 Resonance Pattern Recognition
• Practice the act of recognizing the patterns of resonance and
using curved arrows to push electrons and show their
delocalization.

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
 2.11 Assessing Resonance Structures
• When multiple resonance structures can be drawn, we know a
blend of all of them, the hybrid structure, is the actual structure
of the compound

• Typically, not all of the resonance structures will contribute

equally to the hybrid.

• The following rules, listed in order of importance, allow us to

determine the most significant resonance form(s) for a given
compound (i.e. the MAJOR resonance form)

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
 2.11 Assessing Resonance Structures
RULE 1: The most significant resonance forms have the greatest
number of filled octets

Carbocation doesn’t have In this structure, all atoms

a full octet have an octet, so it is the major
resonance contributor

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
n atom bearing a +2 or −2 charge is highly unlikely. In the example below, the fi
nce form is the best Lewis structure and the largest contributor to the hybrid beca
2.11 Stability of Contributors
filled octets and no formal charges. The second resonance form is still a major c
r since it has filled octets, but it is less significant than the first because it has for
Ruleresonance
. The third 2: The structure
form is awith
minorfewer formal charges
contributor because is more
it has a carbon atom t
n octet significant
⊕
NH2 NH2 ⊝
NH2 ⊝
H C NH H C NH H C NH
⊕

Largest contributor Major contributor Minor contributor

s where there is an overall net charge, as seen in the example below, the creation of n
is not favorable.
The first For
twosuch charged both
structures compounds, theoctets,
have full goal in drawing
but the resonance
first one forms i
ze the charge – relocate
has fewest it to charges,
formal as many different positions
so it is the mostassignificant
possible. resonance
contributor.
⊝ ⊝
O O O
⊝ ⊝
CH3 C CH2 CH3 C CH2 CH3 C CH2
⊕

Insignificant
resonance
Copyright © 2018 John Delocalized
Wiley & Sons, Inc. Allnegative
rights reserved.charge Klein, Organic Chemistry GE
 NH2 NH2 ⊝
NH2 ⊝

2.11 Stability of Contributors

H C NH H C NH H C NH
⊕

Largest contributor Major contributor Minor contributor

If the compound has an overall formal charge, focus only on
where there is anresonance
drawing overall netforms
charge, as seen
that showinthe
thedelocalization
example below,ofthe
thecreation o
s not favorable.
charge For such charged compounds, the goal in drawing resonance form
e the charge – relocate it to as many different positions as possible.
⊝ ⊝
O O O
⊝ ⊝
CH3 C CH2 CH3 C CH2 CH3 C CH2
⊕

Insignificant
resonance
Delocalized negative charge

hings being equal, a structure with a negative charge on the more electronegative e
more significant. To illustrate this, let’s revisit the previous example, in which th
ificant resonance forms. The first resonance form has a negative charge on oxygen
nd resonance form has a negative charge on carbon. Since oxygen is more electrone
bon, the first resonance form is the major contributor:
Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
ificant. To illustrate this, let’s revisit the previous example, in which there are
resonance
Delocalized negative charge
esonance forms. The first resonance form has a negative charge on oxygen, while
gance formahas
equal, structure
first resonance
cant. form is
To illustrate
2.11 Stability of Contributors
a negative
withcharge
thelet’s
this, major
on carbon.
a negative Since
charge
contributor:
revisit
on oxygen is more
the more electronegative
electronegative element
the previous example, in which there are
Rule
onance 3: aThe
forms. structure
first
⊝
withform
resonance a negative charge
has a negative ononthe
charge more
oxygen, while
nce form has a negative
electronegativeO charge
atomonwill
carbon.
beOSince
more
⊝
oxygen is more electronegative
significant, and vice versa
rst resonance form
CH 3 C is the
CH 2 major contributor:
CH3 C CH 2

Major contributor Minor contributor

⊝ We default to Rule 3 here
O O
ive charge will be more stable on the less electronegative
⊝ because
element. more than one
In the follow-
CH3 C CH2 CH3 C CH2
th resonance forms have filled octets, so we consider the location of the has
structure positive
all atoms with
n is less electronegative than oxygen,
Major contributor so contributor
Minor the resonance formawith N+ is and
full octet, the the same
or: number of formal charges
e charge will be more stable on the less electronegative element. In the follow-
resonance forms
H
O
have filled octets, soH we
⊕
O
consider the location of the positive
is less electronegativeH than oxygen, so the⊕ resonance
H form with N+ is the
: N N
H H
Minor
H contributor Major
H contributor
⊕
O O
H ⊕ H
N N
Practice these rules with Skillbuilder 2.8
H H
Minor contributor Major contributor
Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
ectron-rich site
CH3 C NH2

2.11 Stability of Contributors

δ+ δ+

Electron-deficient sites
tes
Practice the Skill 2.26: Draw the significant resonance forms for
kill each
2.26compound below, and indicate the major resonance form.

⊝
NH
O
⊝
O
(a) (b) (c) O
(c) O
H
O H N
H CH3 C C N
(d ) N (e) ⊝ (f ) ⊕

(f ) ⊕
2.27

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
 In the first resonance structure, the bond between the left carbon at
is a double
2.12
2.12bond. The
The Resonance
But in the Hybrid
Resonance Hybrid
second resonance structure,79
Likewise, the bond between the right carbon atom and the middl
that same b

• The in resonance hybrid

one resonance represents
structure and the pi bond
a double of aninallylic
bond the other resona
sonance hybrid,Hybrid
carbocation as being
each of these delocalized over allwith
bonds is shown threeone carbon
solidatoms
line and one
actual structure of this cation is a combination of the individual r
7 that chemists draw resonance structures to deal with the inadequacy of bond-
atter•how that
This
many is are somewhere
consistent
resonance withbetween
MO
structures single
aretheory,
drawn, in bonds
that
they theandpidouble
collectively electrons
represent bonds. Overall
occupy
only
thethat
often called the
bonding
the π bond
resonance is delocalized
MO,hybrid,
which ishas between
no nodes
a combination theall
and
of three
spreadcarbon
isindividual out atomsallin th
across
resonance
ce hybrid iscanconsistent
three be drawn by
atoms. with MO
using theory
partial bondsfor
andthe allylic
partial cation.
charges The π electron
to illustrate
electrons. orbital
As an example,
(Figurelet’s consider
2.4), whichtheis resonance
spread out hybrid
overforallanthree
allyliccarbon
car- atoms
this cation has two resonance structures. These resonance structures are shown
ing that depicts the resonance hybrid.

⊕ ⊕
δ+ δ+
Resonance structures Resonance hybrid

structure,Next,
the bond let’sbetween
consider the the left carbon
formalatom andin
charge thethe
middle carbon
hybrid. Theatom
central carb
in the second resonance structure, that same bond is depicted as a single bond.
the2018resonance
John Wiley & Sons, Inc.structures, so it must also have no formal charge GEin th
etweenCopyright
the© right carbon atom and the middle carbon atom Klein,
All rights reserved. Organicbond
is a single Chemistry
me important 2.13 Delocalized
differences Lone
between lone pairs thatPairs
participate in
ot participate in resonance.
• Localized electrons are NOT in resonance
• Delocalized electrons ARE in resonance (and are more stable)
was a lone pair that is allylic to a π bond. Such a lone pair will
d to• be To be delocalized,
delocalized. Whena lone
an pair
atomofpossesses
electrons amust be adjacent
delocalized loneto
ffected an
byatom with an unhybridized
the presence p orbital
of the lone pair. As an example, consider

O
The lone pair on the nitrogen is
R
R N delocalized because it is next door
to a carbon atom with a p-orbital
R
An amide

would suggest that the nitrogen atom should be sp3 hybridized and
rrect. Instead, the nitrogen atom is actually sp2 hybridized and trigo-
Klein, Organic
Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Chemistry GE
 2.12 Delocalized Lone Pairs
• In one structure, the N is sp3 hybridized, and the other indicates
the N atom is sp2 hybridized. So which is it?

If a lone pair participates in

resonance, then it occupies a
p-orbital

• The lone pair is delocalized, which is only possible through

overlapping p-orbitals. So, the nitrogen must be sp2 hybridized.

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
 2.12 Localized Lone Pairs
• A lone pair does not participate in resonance if it cannot
overlap with an adjacent p-orbital… it is a localized lone pair

The lone pair in pyridine cannot

Overlap with p-orbital on the
Adjacent atom

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE
 2.12 Localized Lone Pairs
• Don’t assume a lone pair is delocalized just because it is next door
to a pi bond.
• As a general rule, you can assume that when an atom possesses a
pi bond and a lone pair, they both will not participate in
resonance.
• And, as always, if there is no p-orbital next door to the lone pair,
then it will be localized

localized
delocalized lone pair
lone pair

localized
lone pair

Copyright © 2018 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry GE