CH 02

Organic Chemistry
Second Edition
David Klein
Chapter 2
Molecular Representations
Copyright 2015 John Wiley & Sons, Inc. All rights reserved.
Klein, Organic Chemistry 2e
2.1 Representing Molecules

There are many ways to represent
molecules
If you were representing a large molecule

with 20 or more atoms, which structure
would be most time consuming to draw?
Which structures give you the most
information about the structure?
Copyright 2015 John Wiley & Sons, Inc. All rights
2-2reserved.
Given that there are three isomers of

propanol (below), which structures above
are adequate to represent only
isopropanol and not its isomers?
Practice with SkillBuilder 2.1

2-3reserved.

To draw large molecules quickly, a
different type of representation is needed
Consider the antibiotic Amoxicillin. Its
Lewis structure looks cluttered, and it
would be very time consuming to draw

2-4reserved.
2.2 Bond-line Structures
The Bond-line structure is easier to read

and to draw

2-5reserved.

It may seem like a foreign language at
first, because many of the atoms are not
labeled
This type of representation is THE main
way that chemists communicate, so it is a
language you MUST master to be
successful in organic chemistry

2-6reserved.

Like Lewis structures, lines are drawn
between atoms to show covalent bonds
Atoms are bonded at angles (zigzag) that

represent the actual geometry of the bond
angles
What is the bond angle for sp3 hybridized
carbon?
Carbon atoms are not labeled, but a

carbon is assumed to be located at every
corner or endpoint on the zigzag.
2-7reserved.

Like Lewis structures, lines are drawn
between atoms to show covalent bonds
Carbon-Hydrogen bonds are omitted.

WHY?
If the H atoms are omitted, how will we
know how many H atoms are attached to a
carbon?

2-8reserved.

Practice identifying the location of and
counting the number of carbon atoms in
the structures below

2-9reserved.

Double bonds and triple bonds are
represented as you might expect
Why is a triple bond written without

zigzagging?

reserved.
2-10

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 we can
assume there are enough to complete the
octet (4 bonds) for each carbon

reserved.
2-11

You should practice bond-line structures
until it becomes natural for you to see all
of the carbon and hydrogen atom
locations.
How many carbon and hydrogen atoms
are in the following molecule?

reserved.
2-12

If you are given a Lewis structure or
condensed structure, you must also be
able to draw the corresponding bond-line
structure
Represent the bond angles with zigzags
Follow VSEPR and spread out the electron pairs

on a central atom

reserved.
2-13

condensed structure, you must also be able
to draw the corresponding bond-line
structure
Single bonds are axes of rotation, so be aware
that they can rotate
Give alternative bond-line structures for the

molecule below

reserved.
2-14

condensed structure, you must also be able
to draw the corresponding bond-line
structure
Heteroatoms (atoms other than C and H) should
be labeled with all hydrogen atoms and lone pairs
attached
NEVER draw a carbon with more than 4 bonds!!

reserved.
2-15

Draw bond-line representations for the
following Lewis structures

reserved.
2-16

Draw bond-line representations for 3 possible
isomers given the formula: C5H9ClO
Draw bond-line structures for 3 different

rotational conformations for the molecule:
CH2CH(CH2)4CH3

reserved.
2-17
2.3 Indentifying Functional

Groups
Bond-line structures allow chemists to
quickly examine how a chemical reaction has
changed a molecule
Compare the condensed formula with the
bond-line structure below for the same
reaction
Which representation makes it more

apparent that the
H is reacting Klein,
to convert
2-18 2
Organic Chemistry 2e

Groups
When certain atoms are bonded together in
specific arrangements, they undergo specific
reactions
chemical
Such
arrangements
of atoms are
called
functional
groups. WHY
are such
groups called
FUNCTIONAL?
reserved.
2-19

Groups
More functional groups are listed in table 2.1
Practice with
conceptual
checkpoint 2.11
reserved.
2-20

with Formal Charge
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
Label all of the formal charges in the
following molecule
Practice with conceptual

checkpoints
2-21

with Formal Charge
Most carbon atoms will have 4 covalent
bonds and no lone pairs to avoid carrying a
formal charge
Sometimes carbon will have a +1 charge. In
such cases, the carbon will only have 3
bonds.
Is there anything2-22especially unstable

about

with Formal Charge
Most carbon atoms will have 4 covalent
bonds and no lone pairs to avoid carrying a
formal charge
Sometimes carbon will have a -1 charge.
Is there anything especially unstable about
CARBANIONS?
If carbon carries a charge in a molecule, the
charge MUST be shown on the bond-line
structure
reserved.
2-23
2.5 Bond-line Structures and

Lone Pair Electrons
Sometimes lone pairs are omitted from bondline structures.

For example
You cant determine the formal charge on the
N atom unless you know how many electrons
there are on the N
It could be
You must ALWAYS draw formal charges on a

bond-line structure to eliminate confusion
reserved.
2-24

Lone Pair Electrons
If the formal charge is indicated on an atom,
you can determine how many lone pairs are
present
To calculate the number of lone pair
electrons for an atom, compare the number
of valence electrons that should be
associated with the atom to the number of
valence electrons that are actually
associated with an atom (section 1.4)

reserved.
2-25

Lone Pair Electrons
How many lone pairs are on the oxygen atom
below?
Oxygen should have 6 valence e-s assigned
to it, because it is in group VIA on the
periodic table.
It is carrying a -1 charge, so it must actually
have one additional electron (6+1=7)
assigned
1 electron is assigned to the oxygen from its
bond with carbon.
2-26 WHY?

Lone Pair Electrons
You can also determine the formal charge on
an O atom by matching its bonding pattern
with its formal charge according to table 2.2

reserved.
2-27

Lone Pair Electrons
The formal charge on a N atoms can be
calculated the same way or by matching its
bonding pattern with its formal charge
according to table 2.3

reserved.
2-28
2.6 3D Bond-line Structures

The vast majority of molecules are 3dimensional, 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

reserved.
2-29

Imagine the thin lines as being flat in the
plane of the board/paper
Dashed and solid wedges to show groups
that point back into the paper or out of
the paper
We will focus on this type of representation in

Chapter 5
reserved.
2-30

Here are some other ways to show 3D
structure
Read the Medically Speaking section of

Chapter 2 to see one example of how 3D
structure is important
reserved.
2-31
2.7 Resonance
Drawing lines between atoms inadequately
represents covalent bonds in molecules with
resonance
Remember from General Chemistry, what is
resonance?
Consider the allyl carbocation:
How is the bond-line structure inadequate in
representing the allyl carbocations TRUE
structure?
reserved.
2-32
2.7 Resonance
Lets look at the hybridization of the carbons
in the allyl carbocation
Calculate the steric number (# of bonds + lone
pairs)
When the steric number is 3, it is sp2 hybridized

reserved.
2-33
2.7 Resonance
If all of the carbons have unhybridized p
orbitals, they can overlap
All three overlapping p orbitals allow the

electrons to move throughout the overlapping
area simultaneously
Thats RESONANCE
reserved.
2-34
2.7 Resonance
From a molecular
orbital point of view,
when the THREE
unhybridized p orbitals
overlap, THREE new
MOs are formed
How many electrons
are in each of the MOs
for the allyl
carbocation?
reserved.
2-35
2.7 Resonance
The allyl carbocation
has a charge of +1.
Which MO is the
missing electron
missing from?
Where is the positive

charge located?

reserved.
2-36
2.7 Resonance
How do we represent the complete picture of
the allyl carbocation provided by valence
orbital and MO theories using a bond-line
structure?
The pi electrons can exist on both sides of the
molecule, so we can use two resonance
contributors to represent the structure
The brackets indicate that both resonance

contributors exist simultaneously
reserved.
2-37
2.7 Resonance
Because neither of the contributors exists
(look at MOs), the average or hybrid is much
more appropriate
vs.
+
+
two contributors
resonance hybrid
How is a resonance arrow different from
equilibrium?
Analogy: a nectarine is a hybrid formed by
reserved.
2-38
2.7 Resonance
Resonance makes a molecule MORE stable
Delocalization of electrons
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.
+
reserved.
2-39
+
2.8 Curved Arrows in

Resonance
Throughout Organic Chemistry, we will be
using curved arrows to show electron
movement
The sooner you master this skill, the easier
the course will be
Curved arrows generally show electron
movement for pairs of electrons
The arrow starts where the electrons are currently
located
The arrow ends where the electrons will end up
after the electron movement
We will explore curved arrows to show other

reserved.
2-40

Resonance
Rules for using curved arrows to show
RESONANCE
1. Avoid breaking a single bond
Single bonds can break, but NOT in

RESONANCE
Resonance occurs for electrons existing in
overlapping p orbitals, while electrons in
2
3
single bonds are2-41overlapping sp,
sp
,
oder
sp

Resonance
RESONANCE
2. Never exceed an octet for 2nd row elements (B, C,
N, O, F)
Atoms in the 2nd row can only have four 2nd

energy level orbitals holding a max. of 8
electrons
Examples of arrows that violate rule 2.

reserved.
2-42

Resonance
RESONANCE
3. 2nd row elements (B, C, N, O, F) will rarely but
sometimes have LESS than an octet
What will the resonance hybrid look like for

this structure?
reserved.
2-43
2.9 Formal Charge in

Resonance
When using curved arrows to show
RESONANCE, often structures will carry a
formal charge that must be shown
Draw the resonance contributor indicated by
the arrows below
Are any of the rules violated?

Show any formal charges on the contributors
reserved.
2-44
2.9 Formal Charge in

Resonance
In the resonance, the arrows tell us how to
move the electrons to create the other
contributor
Draw arrows showing the resonance in the

reverse direction
You can also think of the arrows as showing
the direction that charge will flow
reserved.
2-45
2.10 Patterns in Resonance

There are 5 main bonding patterns in which
resonance occurs. Recognize these patterns
to predict when resonance will occur
1. Allylic lone pairs
2. Allylic positive charge
3. Lone pair of electrons adjacent to a positive
charge
4. A pi bond between two atoms with different
electronegativities
5. Conjugated pi bonds in a ring
We will see many examples in the next few

slides
reserved.
2-46

Vinyl and allyl refer to positions directly
bonded to or one atom away from a C=C
double bond
Label the vinylic chlorides and the allylic

chlorides

reserved.
2-47

1. Identifying allylic lone pairs
. Circle all of the allylic lone pairs
. Draw arrows on each structure to show

resonance

reserved.
2-48

1. Identifying allylic lone pairs
. For each, show the resulting resonance
contributor and all formal charges
. Practice with conceptual check point 2.25

reserved.
2-49

2. Dealing with allylic positive charge
. Only one curved arrow is needed
. If there are multiple double bonds

(conjugated), then multiple contributors are
possible. Show the resonance contributors
and curved arrows below
. Draw a resonance hybrid

. Practice with conceptual
checkpoint
2.26
2-50

3. A lone pair adjacent to a positive charge
. Only one arrow is needed
. Explain how the formal charges are affected
by the electron movement in the following
examples

reserved.
2-51

3. A lone pair adjacent to a positive charge
. Consider the resonance in the NITRO group
. Why cant ONE arrow be used to cancel out
the formal charge and create a resonance
contributor?
. Draw all possible resonance contributors
. Practice with conceptual checkpoint 2.27

reserved.
2-52

4. A pi bond between atoms of different
electronegativity
. The pi electrons will be more attracted to
the more electronegative atom
. Explain how the formal charges are created
by the electron movement in the following
examples

reserved.
2-53

5. Conjugated pi bonds in a ring
. Each atom in the ring MUST have an
unhybridized p orbital that can overlap with
its neighbors
. Electrons can be shown to move clockwise

or counterclockwise
. What type of motion do the electrons
actually have?
reserved.
2-54
Summary figure 2.5
Practice with conceptual checkpoint 2.32

reserved.
2-55
Show all of the resonance contributors for

the following molecule
Notice that carbons with 4 bonds (sp3)

isolate areas of resonance from one another
reserved.
2-56
2.11 Stability of
Contributors
Remember our nectarine analogy. Is a

nectarine more like a peach or more like a
plum?
What if we made a fruit that was 65%
peach, 34% plum, and 1% kiwi? How would
that look?
Similarly, there are many molecules that
have multiple resonance contributors where
not all resonance structures contribute
equally
The resonance hybrid will most resemble
the more stable2-57contributor(s) Klein, Organic Chemistry 2e
2.11 Stability of
Contributors
How do we assess the stability of resonance
contributors?
1. Formal charge generally DECREASES stability,
especially a +1 charge on an electronegative
atom or -1 on a low electronegativity atom
2. COMPLETE OCTETS INCREASE stability
Draw the three resonance contributors for

acetic acid
Assess the stability of each contributor, and

draw a resonance hybrid
reserved.
2-58
2.11 Stability of
Contributors
1. Formal charge generally DECREASES stability
2. A +1 charge on an electronegative atom or -1 on
a low electronegativity atom is especially
unstable
Draw the three resonance contributors for

the acetate ion


reserved.
2-59
2.11 Stability of
Contributors
1. Formal charge generally DECREASES stability
2. A +1 charge on an electronegative atom or -1 on
a low electronegativity atom is especially
unstable
Draw the resonance contributors for the

following molecule

reserved.
2-60
2.11 Stability of
Contributors
The octet rule is usually a bigger factor than
formal charge when assessing stability

For each structure, assess the stability of
each contributor, and draw a resonance
hybrid

reserved.
2-61
2.12 Delocalized vs.

Localized
Localized electrons are NOT in resonance
Delocalized electrons ARE in resonance
Delocalization increases stability
There are a couple ways to recognize

electrons that are delocalized through
resonance?
1. To be delocalized, electrons must exist in an
unhybridized p orbital that can overlap with p
orbitals on neighboring atoms
2. To be delocalized, electrons must be on an sp or
sp2 hybridized atom

reserved.
2-62

Localized
Does the delocalization of the electrons in
the amide create a more or less stable
contributor?
Delocalization must be a very stabilizing

force if it can favor sp2 hybridization over
sp3 even when the delocalization doesnt
involve two equally
stable contributors
2-63

Localized
To allow for delocalization (resonance),
some atoms that would normally be sp3 will

become sp2 hybridized
Calculate the steric number and predict the
hybridization for Nitrogen atom of an amide
If the Nitrogen atom were sp3, its lone pair
of electrons couldnt engage in resonance
The Nitrogen of an amide will be sp2
hybridized
In this case, the stability of the delocalization

outweighs the stability difference between sp2
and sp3

reserved.
2-64
Klein, Organic
Chemistry 2e
3

Localized
The sp2
hybridization of the
nitrogen atom
causes it to be
trigonal planar
rather than
tetrahedral
To be delocalized,
all three atoms
involved MUST have
p orbitals
2-65
overlapping

Localized
Generally, lone pars
adjacent to a C=C double
bond are capable of
resonance, but not in this
case.
The electron movement above does not

violate any of our rules, so why cant the
Nitrogens lone pairs be delocalized? - see
next slide
reserved.
2-66

Localized
Recall that delocalized electrons must exist
in an unhybridized p orbital overlapping

with p orbitals on neighboring atoms
The Nitrogens
lone pair is
positioned
perpendicular to
the plane where
the other pi
electrons reside
Practice with
SkillBuilder 2.9
reserved.
2-67
Additional Practice Problems

How many carbon and hydrogen atoms
are in the following molecule?

reserved.
2-68

Draw the bond-line structures from the
following formulas:
C(CH3)3CN
Cl2CH(CH2)5CO2H

reserved.
2-69

Fill in any necessary formal charge on the
molecule below

reserved.
2-70

Fill in any necessary lone pairs in the
structure below

reserved.
2-71
Show all of the resonance contributors for

the following molecule and draw the
resonance hybrid

reserved.
2-72

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Organic Chemistry

Klein, Organic Chemistry 2e

2.1 Representing Molecules

If you were representing a large molecule

Klein, Organic Chemistry 2e

2.1 Representing Molecules

Given that there are three isomers of

Practice with SkillBuilder 2.1

Copyright 2015 John Wiley & Sons, Inc. All rights

Klein, Organic Chemistry 2e

2.1 Representing Molecules

Copyright 2015 John Wiley & Sons, Inc. All rights

Klein, Organic Chemistry 2e

2.2 Bond-line Structures

The Bond-line structure is easier to read

Copyright 2015 John Wiley & Sons, Inc. All rights

Klein, Organic Chemistry 2e

2.2 Bond-line Structures

Copyright 2015 John Wiley & Sons, Inc. All rights

Klein, Organic Chemistry 2e

2.2 Bond-line Structures

Atoms are bonded at angles (zigzag) that

Carbon atoms are not labeled, but a

Klein, Organic Chemistry 2e

2.2 Bond-line Structures

Carbon-Hydrogen bonds are omitted.

Copyright 2015 John Wiley & Sons, Inc. All rights

Klein, Organic Chemistry 2e

2.2 Bond-line Structures

Copyright 2015 John Wiley & Sons, Inc. All rights

Klein, Organic Chemistry 2e

2.2 Bond-line Structures

Why is a triple bond written without

Copyright 2015 John Wiley & Sons, Inc. All rights

Klein, Organic Chemistry 2e

2.2 Bond-line Structures

Copyright 2015 John Wiley & Sons, Inc. All rights

Klein, Organic Chemistry 2e

2.2 Bond-line Structures

Practice with SkillBuilder 2.2

Klein, Organic Chemistry 2e

2.2 Bond-line Structures

Follow VSEPR and spread out the electron pairs

Copyright 2015 John Wiley & Sons, Inc. All rights

Klein, Organic Chemistry 2e

2.2 Bond-line Structures

Give alternative bond-line structures for the

Copyright 2015 John Wiley & Sons, Inc. All rights

Klein, Organic Chemistry 2e

2.2 Bond-line Structures

NEVER draw a carbon with more than 4 bonds!!

Klein, Organic Chemistry 2e

2.2 Bond-line Structures

Copyright 2015 John Wiley & Sons, Inc. All rights

Klein, Organic Chemistry 2e

2.2 Bond-line Structures

Draw bond-line structures for 3 different

Copyright 2015 John Wiley & Sons, Inc. All rights

Klein, Organic Chemistry 2e

2.3 Indentifying Functional

Which representation makes it more

2.3 Indentifying Functional

Klein, Organic Chemistry 2e