I.

Structure & Bonding

Bonding is the joining of two atoms. Through bonding, atoms achieve a complete
outer shell of valence electrons.
The Octet Rule: Atoms transfer or share electrons in such a way to attain a filled
shell of electrons (the electron configuration of a noble gas such as He, Ne, or Ar.
Duet
H: 2Nd for filled valence shell He configuration
2nd rowrule
octet elements:
8 e for filled valence shell neon configuration
There are two ways that atoms can interact to attain noble gas configurations:
Ionic Bonding & Covalent Bonding

A. Ionic Bonding
Atoms attain a filled valence shell by transferring electrons from one to another.

note O
Li Li
shhook
now shows
ansfer of
e Hoenig Ihrig
HÉra9 h in 8981749 ftp.cfectrostatic
Ioniccompletely transferred
bonding is seen with atoms of widely differing electronegativities:

I
Increasing VIII
H He
2.2 II III IV V VI VII
Li Be B C N O F Ne
1.0 1.6 1.8 2.5 3.0 3.4 4.0
Na Mg Al Si P S Cl Ar
0.9 1.2 1.5 1.9 2.2 2.6 3.2
K Ca Br Kr
0.8 1.0 3.0
I Xe
2.7

1
Fentativity
 Y

 In general: If electronegativity difference is greater than about 1.8, the

electron will be transferred completely (the bond will be ionic.)

B. Covalent Bonding
electronegative diff 1.8
Atoms attain a filled valence shell by sharing electrons.
shared electrons ie H H
bonds pictured as lines
H H H H H H
or H H Ei
2
each atom has filled shell
 This type of bonding is seen with atoms of the same or closer electronegativities.

Look at how C, H, N, O, & the halogens satisfy the octet rule:

Atom Valence To Complete Number of Bonds in Neutral

Electrons Shell Compounds

Carbon (C) 4 4 e– needed 4 C C C

N
Nitrogen (N) 5 3 e– needed 3 N N N

2 O O
Oxygen (O) 6 2 e– needed

Hydrogen (H) 1 H 1 e– needed 1 H

1 Cl
Halogens 7 1 e– needed

EZ way to remember: HONC-1234 rule:

for neutral compoon
Hydrogens and Halogens make 1 bond
Oxygen makes 2 bonds
Nitrogen makes 3 bonds
Carbon makes 4 bonds
2
When C, H, N, O, & the halogens deviate from the HONC rule, they are said to have
a formal charge. A formal charge is a charge associated with an atom that does not
exhibit the expected number of valence electrons (section 1.5 Klein).

Atom # Bonds # Bonds to Atom when # Bonds to Atom when

to neutral Cationic Anionic
atom
3 bondsw charge 3 bonds w charge
Carbon 4 3 C C 3 C C C
(C)
4 bonds w t charge 2 bonds w charge
Nitrogen 4 N N N 2 N N
3
(N)
3 bonds wt charge 1 bond with charge
Oxygen 2 3 O O O 1 O
(O)

How do we know this?

Look at carbon, for example:

neutral carbon has 4é in valence shell
Ct has 3 e can only bond w 3 atoms

c has 5é bonds to 3 atoms

like nitrogen
Practice this skill: PP1

Formal charge can be determined in three ways:

1. Memorize the chart above.

2. Calculate by using a formula.

Formal charge = (# valence e-s) - (1/2 # bonding e-s) - (# nonbonding e-s)

3. Compare the expected number of valence electrons to the actual number of

electrons in the structure.

3
Examples: Assign formal charge to any atoms that are charged.

H H
H N C H
H H

H O H
H

H
C
H H

A more complicated example:

H H O
H C C C H
H C C O
H H

Practice this skill: PP2

Exceptions to the octet rule:

1. Third row and higher elements - These have d orbitals available for bonding,
so they sometimes exceed an octet in their valence shell.
Examples: Sulfuric Acid (H2SO4) and Phosphoric acid (H3PO4)

O O
H O S O H H O P O H
O O H

4
 2. Molecules with open shells - sometimes there are not enough electrons to
provide an octet!

open shell compounds: can accept a pair of electrons to complete an octet

II. Representation of Structure

There are different ways to represent the structures of molecules, and some ways
provide more information than others:

Example:
C2H5O

This is the molecular formula for the compound. It is:

• Useful for calculating molar mass, but gives no information about how atoms
are bonded together.
• The molecule has an overall positive charge, but we don’t know which of the
atoms has a charge.

A. Condensed structure

This is the condensed structure of the same compound:

CH3CHOH

Condensed structures are a shorthand way of drawing molecules where some or all
of the covalent bonds are left out. They are drawn in a way that gives information
about how the atoms are bonded together.

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 Guidelines:
• All atoms are drawn in, but bond lines are generally omitted.
• Atoms are usually drawn next to the atoms to which they are bonded.
• Parentheses are used around similar groups bonded to the same atom.
• Lone pairs are usually omitted.
• Formal charges are shown on the atom to which they belong.

Examples:

CH3C(CH3)2CH2Cl

CH3CHO

CH3COCH3 or CH3C(=O)CH3

CH3CO2H or CH3COOH

CH3CH=CHCO2CH3

Practice this skill: PP3

B. Lewis Structure

Lewis structures give connectivity and the location of all bonding and non-
bonding electrons as well as formal charges. They do not give information about
the three-dimensional (3-D) orientation in space.

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Lewis structure of sample compound:

Lone pairs are required in Lewis Structures! In most other structures they are
left out and “understood”, which means that they are implied: you understand that
they are there, you are just leaving them out to save time.

C. 3-D Structures
3-D give the three-dimensional orientation in space and all formal charges.
Lone pairs are optional.
= in the plane of the paper
= out of the plane of the paper
= behind the plane of the paper

D. Skeletal (Bond-Line) Structures

Skeletal structures are a simplified way of drawing more complex molecules,
especially those containing rings.
Guidelines(section 1.2 Klein):
1. Assume there is a carbon at the junction of any 2 lines or at the end of any line.
2. Assume there are enough hydrogens around each carbon to make it tetravalent.
3. Draw in all heteroatoms (atoms other than C) and the hydrogens directly
bonded to them.
4. Carbon atoms in a straight chain are drawn in as a zig-zag.
5. Lone pairs are often left out and are “understood.”
6. Always include formal charges!

Skeletal structure of sample compound:

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Example 1: Draw skeletal structures of the following compounds:
H
H H O H H H O H O H
H C C C C C O C H H C C C C C N CH3
H C H H H H H H
H H H

Example 2: Redraw all of the following compounds showing all atoms, lone pairs
and formal charges
H
O

 Notice: Lone pairs are not required in skeletal structures! They are implied.
You must be able to fill them in where necessary (section 1.6 Klein).
 Keep in mind: When drawing a molecule, either show all of the hydrogens and
all of the carbons or draw skeletal structure. You cannot draw the carbons
without drawing the hydrogens (section 1.3 Klein)!
C
NOT: C C C
C C C
C
Practice this skill: PP4

III. Drawing Lewis Structures

One of the most essential skills that you need for success in organic chemistry is the
ability to draw Lewis structures and resonance structures. A lot of practice will make
this ability second nature!

8
To Draw Lewis Structures:

Traditional method:
1. Arrange atoms in the proper orientation (condensed structures will give
information about how atoms are bonded together).
2. Sum valence electrons for all atoms. For charged molecules: Add one electron
for each negative charge, and subtract one electron for each positive charge.
3. Distribute electrons by placing bonds between atoms (one bond is two
electrons). Use remaining electrons to satisfy the duet rule for H and the octet
rule for second row elements. Third row elements can exceed an octet.
4. If all valence electrons are used and an atom does not have an octet, form
multiple bonds where possible.

• Maximize the number of bonds without exceeding the octet rule.

• Assign formal charge to any charged atoms.
• Be sure to draw in all lone pairs!

Alternative method: Use the HONC-1234 rule for neutral compounds.

 A combination of the traditional and alternative method is also useful!

Recommendation: If you have a charged compound, always count electrons!

Example 1: Write the Lewis structure for CH3Cl

2 ways:
1. Traditional method:

9
 2. Shortcut: Follow the HONC-1234 rule for neutral molecules. For charged
structures, use the table given.

Example 2: Write the Lewis structure for ethylene (CH2CH2).

Example 3: Write the Lewis Structure for (CH3)3C+

Practice this skill: PP5

IV. Resonance Structures

Sometimes there is more than one Lewis structure that you can draw for a molecule.
When this happens, the multiple Lewis structures are called resonance structures. In
organic chemistry, we are very interested in resonance structures, even minor ones,
because they give a more complete picture of a molecule, and they allow us to predict
reactivity. The ability to draw resonance structures is critical to your success in
organic chemistry. Practice, practice, and practice will make this second nature!

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Example: Write the Lewis Structure for [CH3CHOH]+

Curvy arrows: show movement of a pair of electrons.

Tail: begins at the current position of electrons
Head: new position of electrons

Important points about this example:

The above molecule can be represented by more than one Lewis structure. The two
Lewis structures are resonance structures for the same molecule.

H H H H
H H
H C C O H C C O
H H

* Resonance Structures differ only in the arrangement of electrons, NOT in the

connectivity.
* The actual structure of the molecule is a resonance hybrid of the 2 structures.

Arrow Review:
resonance arrow
equilibrium arrow
reaction arrow
curvy arrow - shows movement of a pair of electrons
fishook arrow - shows movement of a single electron

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Analogy:

One way we can represent the resonance hybrid:

 This hybrid structure gives a more accurate representation of the true

distribution of electrons in the molecule. Notice in the hybrid there are two
atoms that share the positive charge, that is, there are two sites in the molecule
that are electron deficient.

Important points about resonance structures:

 Each resonance structure does not adequately depict the true structure of a
molecule - only the hybrid does.
 Resonance structures are not in equilibrium with each other.
 Resonance structures are not isomers of each other. Isomers differ in the
arrangement of atoms and electrons, whereas resonance structures differ only in
the arrangement of electrons.

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 H H H O H H O
H C C O and H C C O H C C H and H C C H
H H H

 These two resonance structures are not equivalent in energy!

H H H H
H H
H C C O H C C O
H H

V. Curvy Arrows: The Tools for Drawing Resonance Structures

Curvy arrows are powerful tools for drawing resonance structures. Learning to
correctly use curvy arrows will not only help you with resonance structures, but will
also help you with mechanisms, which are extremely important in organic chemistry.

Tail Head

A curvy arrow always comes from a pair of electrons (either electrons from a lone
pair or a bond) to an electron deficient site.

H O H
H
H H

13
 H
H H

H H

Arrows do NOT come from atoms or charges!

H
H O H H H
H
H H H H

The head of the arrow must either point directly in between two atoms to form a
bond, or it must point to an atom to form a lone pair:

H
H H

H H

A. The Two Commandments: What Not To Do!

When drawing arrows between resonance structures, DON’T break the Two
Commandments (section 2.3 Klein):

1. Thou shalt not break a single bond when drawing resonance structures.
2. Thou shalt not exceed an octet for second-row elements.

That doesn’t mean you can’t have less than an octet, which leads to the King
Corollaries:

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Corollary 1: It is okay to have carbon without an octet in a resonance structure, but
never draw O, N, or the halogens without an octet.
Corollary 2: Never draw a resonance structure with a 2+ or a 2− charge

Let’s look at each of the commandments:

Commandment 1: When drawing resonance structures, don’t break single bonds:

Commandment 2: Don’t exceed an octet for 2nd row elements, and don't exceed a
duet for 1st row elements
Bad arrow pushing:
H
O C H O N H H3C N O
H H O

Pitfall: If you use skeletal structures, it is easy to break an octet without realizing it!

King Corollary 1: It is common to have carbon without an octet in a resonance

structure. A more electronegative atom than carbon, such as O, N, and the halogens
should NOT be drawn with less than an octet!

15
Okay:
O

Not okay:
O

 Generally speaking, when you are breaking a π bond, the electrons go to the
more electronegative atom.

Q: Why is it okay to have carbon with less than an octet but it is not okay to have
oxygen with less than an octet?
A:

King Corollary 2: Avoid drawing a resonance structure with a 2+ or a 2− charge

Not okay:

N N N

Practice this skill: PP6

B. Drawing Good Arrows (Klein section 2.4)

Now that you know good arrow pushing and bad arrow pushing, let’s practice
drawing correct arrows between two resonance structures.

 Remember: The tail of the arrow must come from a pair of electrons (from a bond
or lone pair) and the head of the arrow must point midway between two atoms (if
you are forming a new π bond) or at an atom (if you are forming a new lone pair).

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 Make sure to draw all lone pairs before you begin drawing resonance structures!!

Example 1: Draw curvy arrows to convert the 1st resonance structure into the 2nd.

O O

If you did this instead:

Example 2: Draw curvy arrows to convert the 1st resonance structure into the 2nd.

If you did this instead:

Practice this skill: PP7

C. Formal Charges in Resonance Structures

In the previous section a pair of resonance structures were drawn and you had to
fill in arrows. In this section we’ll practice drawing resonance structures when the
arrows are drawn, but the second resonance structure is not given.

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Example 1:

Don’t forget to write formal charges for any charged atoms! We have talked about
three ways to figure out formal charge:
1. Memorize the charged atoms chart (page 4 notes)
2. Use the formula
3. Compare expected number of valence electrons to the actual number of
electrons in the structure.
With curvy arrows, there is a fourth way to figure out formal charge:
4. Follow the electron trail. For the above example, the logic goes like this:
Oxygen has a zero charge and owns both electrons in the lone pair that is
moving. As soon as the lone pair moves to make a new π bond, oxygen no
longer “owns” both electrons – it now shares the pair of electrons with carbon,
and only “owns” one of the electrons now. Therefore it has a formal charge of
+1 because it has lost an electron.

Likewise, the two carbons share the electron pair in the π bond and both are
uncharged. Once these electrons move onto the second carbon, this carbon
now “owns” both electrons, thereby gaining an electron and having a formal
charge of −1. The carbon bonded to oxygen didn’t gain or lose an e− because
it started out as part of a double bond, and ended up part of a double bond.

Choose which strategy you like best! It is important to have choices because
everyone has a different learning style.

Example 2:
O

Practice this skill: PP8

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VI. Draw Resonance Structures Step-by-Step

Our ultimate goal is to be able to draw a Lewis structure of a molecule plus all
important resonance structures, without breaking any rules. We have talked about the
rules, and now we are going to learn to recognize parts of the molecule that will
exhibit resonance.

Remember: When drawing resonance structures, we use curvy arrows to move

electrons from π bonds or lone pairs (breaking single bonds breaks the first
commandment). That means when we are looking for parts of a molecule that exhibit
resonance, we will look for π bonds and lone pairs!

Look for:

Then ask yourself:

1. Can I convert any lone pairs unto π bonds without violating the two
commandments or corollaries?
2. Can I convert any π bonds into lone pairs without violating the two
commandments or corollaries?
3. Can I convert any π bonds into π bonds without breaking the two
commandments or corollaries?

Example 1:

H
N

19
Example 2:

Example 3:

20
Example 4:

Example 5:

Practice this skill: PP9

VII. Drawing Resonance Structures By Looking for Patterns

I would take a very long time if we had to go through this analysis every time we had
to draw resonance structures. Fortunately, there are patterns that we can look for that
will simplify and speed up this process. There are five patterns that you should learn
to recognize to become proficient in drawing resonance structures (Klein 2.7):
1. A lone pair next to a π bond
2. A lone pair next to a positive charge
3. A π bond next to a positive charge
4. A π bond between two atoms, where one of those atoms is electronegative.
5. Alternating π bonds and single bonds in a ring

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 1. A Lone Pair Next to a π Bond

OH
O N O

O N

Note: The lone pair needs to be directly adjacent to the π bond. If it is one more
atom over, you will not able to draw a resonance structure.

vs.

Practice this skill: PP10

22
 2. A lone pair next to a positive charge

O N
O

There is one compound where this strategy doesn’t work:

H3C N O
O

so for this compound, we look for the lone pair adjacent to a π bond:

H3C N O
O

Practice this skill: PP11

3. A π bond next to a positive charge

Practice this skill: PP12

23
 4. A π bond between two atoms, where one of those atoms is electronegative.

A π bond between like atoms is generally not broken:

Practice this skill: PP13

5. Alternating π bonds and single bonds in a ring

Double bonds separated by single bonds are said to be conjugated:

When the conjugated double bonds are in a ring, the electrons can be moved
around in a circle:

Putting it all together: You are now ready to draw your own resonance structures by
looking for the five patterns!
Practice this skill: PP14

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VIII. Assessing the Relative Importance of Resonance Structures

H H H H
H H
H C C O H C C O
H H

Q. What makes a good resonance structure?

A. The best resonance structures are the most stable!

Look for the following structural features (in order of importance):

Rule #1: Resonance structures w/ more bonds and fewer charges are more stable.
Rule #2: Resonance structures in which every atom has an octet are more stable.
Rule #3: Resonance structures that place a negative charge on a more
electronegative atom are more stable.

 Remember N, O, Halogens must have octets!

 Don’t have resonance structures with a 2+ or 2− charge! These are extremely
minor and should not be included.

Practice this skill: PP15

IX. Using Hybrid Structures and Electrostatic Potential Maps to Visualize the
charge Distribution in a Molecule

A hybrid structure gives a close approximation of the true structure of a molecule. It

shows electron rich and electron poor parts of the molecule. It does not do a good job
of showing weighted charges.

25
To draw a hybrid structure:
1. Draw all of the single bonds in the molecule.
2. Draw dotted lines for π bonds that are changing location or not showing in
every resonance structure.
3. Draw partial charges for charges that are changing location or not showing in
every resonance structure using the symbol delta: δ+ and δ−
4. Το make this easier, you can leave out lone pairs.

Example 1 (from page 11 notes):

H H H H
H H
H C C O H C C O
H H

Limitation of hybrid structures: Charges are not weighted. What do I mean by

weighted? Because the second resonance structure is a better resonance structure that
the first one, it means that this structure will contribute a larger amount to the hybrid,
and therefore, in the true representation of this compound, the partial charge on
oxygen will be larger than the partial charge on carbon.

A good way of showing weighted charges is to use an electrostatic potential map.

Electrostatic potential maps are easily drawn using Spartan. Electrostatic potential
maps are very helpful in showing how the charge is distributed in a molecule. The
colors on a potential map indicate the degree to which a molecule or an atom in a
molecule attracts charged particles. The colors can also be used to estimate charge
distribution.

red < orange < yellow < green < blue

26
Look @ the electrostatic potential maps for ethoxide ion and carboxylate ion:

O O

O O

Example: Draw resonance structures for the following two molecules, rank the
resonance structures in order of importance then draw a hybrid structure for each.
Compare the hybrid structure to the electrostatic potential maps for these compounds
above.

Practice this skill: PP16

Then PP17

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