Honors Organic Chemistry I

Lecture One
Representing the Structures
of Organic Molecules
 Why do we care?
The ability to make new molecules with
predictable structures and properties is one
aspect that sets organic chemistry apart from
other branches of chemistry, physics and
biology.

The essential processes of biology are

chemical reactions of organic molecules.
Both quotes are from Thomas Sorrell, Organic Chemistry,
page one.
 Why do we care?
The ability to make new molecules with
predictable structures and properties is one
aspect that sets organic chemistry apart from
other branches of chemistry, physics and
biology.
In order to understand and predict the properties
of organic compounds, we must understand their
structures.
Is anatomy destiny?
Chemical Bonding and Structure
Why do bonds form?
Bonding models: Lewis Structures
Drawing simple Lewis structures
Multiple bonds and complex Lewis
structures
All about formal charges
Resonance structures and their meaning
Problems with Lewis structures

Functional Groups
 Bonding
When do bonds form?
Bonds form when the interaction of
atoms lowers their net energy.
Now consider two cases for
bonding:
He , He vs. HeHe

lower E

higher E
NO BOND
H ,H vs. HH
higher E

lower E BOND
 How do bonds form?
Ionic bonding is based on:
the transfer of electrons, which introduces
charge separation: My+ and Xn.
These new ions attract each other.
The energy of attraction is
E = the bonding energy
defined by Coulombs law.
k = the electrostatic force
Coulombs law: constant (a proportionality const.)
q1q2
____ q1, q2 = charges of the ions
E=k
r r = the distance separating
the ions

The bond is stronger if the inter-ionic distance (r) is small.

The bond is stronger if the charge magnitudes (q1,2) are large.
How do bonds form?

Covalent bonding
Electrostatic forces still apply
Electrons are shared
Orbital overlap replaces electron transfer

Electron density is concentrated in

the area of orbital overlap, where
electrostatic attractions are largest.

We will return to this model in the next lecture.

Bond Energy Diagram It is important that you
understand this diagram
A bond is an energy hole that atoms
fall into when they come together and
share electrons. The atoms are bonded
because they dont have the energy to
get out of that hole!
E 0

Notice that the

Bond bond energy
energy is negative.
l

Internuclear distance It is energy that the

r
two atoms released as
the bond was formed.
Bond Energy Diagram
A bond is an energy hole that atoms
fall into when they come together and
share electrons. The atoms are bonded
because they dont have the energy to
get out of that hole!

Bond energy is energy that

the bonded atoms dont have !
Bonding Models
It is common to start with a localized
model of covalent bonding (the electrons
are localized between two nuclei):
Lewis structures

These are electron dot pictures

The bonds are represented by shared
electron pairs.
Only outer shell (valence shell) electrons
are depicted.



 Lewis Symbols for Atoms
O: 1s2 2s2 2p4
O or O
valence electrons

B: 1s2 2s2 2p1

B
valence electrons

Xe: [Kr] 5s2 4d10 5p6

Xe
valence electrons

The valence electrons are defined here as the s and p

electrons with the highest principal quantum number.
Problem 1-1
Write the electron configuration, identify the
valence electrons, and draw the Lewis
symbol for the following atoms:
a) S
b) Cl
c) N
d) P
The Octet Rule

Significant stability is associated with full valence

shells: ns2 np6 8 electrons
These 8 electrons are the octet.
Noble gas stability is a prime example.
The octet rule also governs ion formation:

Atoms tend to gain or lose electrons in
forming ions until they achieve a valence shell
octet.
Covalent Bonding:
Building molecules by sharing electrons
in Lewis structures:

H O H

H O H H O H
O is like Ne H is like He
 Covalent Bonding: CH4
First, write out all the atoms, each
with the proper # of electrons.

4 H C
Then pair one H
electron with each of
the C electrons.
The bonding pairs can
also be represented
H H
by single lines.

H C H H C H
H H
This type of representation is usually
called a Kekul structure.
Problem 1-2
Write the Lewis structure for each set of atoms.
Then figure out how they might bond together
covalently to form a stable compound.
a) C, Cl, Cl, F, H (central C atom)
b) N, 2 H, Cl (central N atom)
c) P and H (use as many H atoms as you need)
d) 2 C and 6 H
e) O, F, H (central O)





 Multiple bonds
C2H4
In some molecules the atoms form double or triple bonds.
First, write out all the atoms
with the proper #s of electrons. C C H H H H
Second, join the two carbons
by forming one electron pair. (WHY?)

H C C H
Two electrons

H H remain unpaired!
Third, pair one H and
its electron with an
unpaired electron on Lets double check this.
one of the two Cs.




 Multiple bonds
C2H4 Lets double check this.
...using a
C C H H H H different
method.
First, line up the atoms Second, add the Third, take the as
the way you expect electrons in pairs to yet unpaired
them to bond. make the bonds. electrons... and form a
second C-C bond.

H C C H H C C H H C C H

H H
H H H H
The pairings are The final structure
confirmed. is equivalent to:

HC CH

Double bonds are actually fairly common.

H H
 Multiple bonds







triple bonds
C2H2

C C H H

HC C H H C C H
Same as

HC CH
Acetylene
Problem 1-3
Draw the Lewis structure for each of the atoms
in the formulas below. Then draw the Lewis
structure for each molecule.
a) HCN (central C)
b) CH2O (central C)
c) C2Cl2
d) NHO (central N)
 Lewis Structures of Ions
SO32

S O O O

OS O OS O OS O
O O
O

O S O
O

Where are the charges?

 Formal Charge
Some molecules dont seem to behave themselves
very well. for example :
PCl3O

Cl

Cl P O

Cl

If we assign the
electrons:
 Formal Charge
Some molecules dont seem to behave themselves
very well. for example :
PCl3O
Cl



7 valence electrons

Cl P +
O -

7 valence electrons 4 valence electrons 7 valence electrons
... not 5! ... not 6!
If we assign the
Cl

electrons: So P is positive,
7 valence electrons and O is negative.
 Formal Charge
Some molecules dont seem to behave themselves
very well. for example :
PCl3O
Now if we reconstruct
the molecule:
and draw the bonding
Cl electron pairs as lines...
+ -
Cl P O and add the formal
Cl charges...
and remove the
we get a standard Kekul model, non-bonded
with formal charges. electrons...
Formal Charge
Features of formal charge:
They are not really full charges
Cl (but electron bookkeeping assigns
+ - them as full unit charges).
Cl P O
The sum of formal charges = the
Cl overall molecular/ionic charge.
Determination of formal charges
is required whenever any atom has
more or fewer than the typical
number of bonds.
 Formal Charge (FC)
A formula for calculating formal charges:

Number of valence Number of Number of

electrons in the 1/2 bonding nonbonding
FC = free atom electrons electrons

Cl For P: FC = 5 1/2(8) 0 = +1
+ -
Cl P O
For O: FC = 6 1/2(2) 6 = 1
Cl [But feel free to do this without the formula!]

Prove to yourself that for Cl, FC = 0

 Lewis Structures of Ions
SO32 You remember this...

S O O O

O S O
Wheres the charge?
O
Problem 1-4:
Assign formal charges to SO32.
Problem 1-5

Draw Lewis structures for the following ions.

Include formal charges.
a) NO3
b) HCO3 (There is no C-H bond.)
c) PO43
Resonance Structures
An apparent flaw in the Lewis bonding model appears when
one tries to draw the Lewis structure for O3. (ozone)
Heres the problem:
We could just as O O O

the two terminal oxygen
easily have drawn atoms are known to be
either of these:
O O O chemically equivalent.

Each of these two Lewis structures is valid, but neither can fully
represent the molecule. The solution is to call each a resonance
structure, and to state that the real structure is a hybrid:

O O O O O O

[Where are the

This double-headed formal charges in
these structures?]
arrow is reserved for
resonance hybrids only!
Resonance Structures
Resonance is NOT a back and forth phenomenon.
It is more like a dragon and a unicornrepresenting
a rhinoceros.
More Resonance Structures
The carbonate ion, CO32 . . .
2-

O

C C C
O O O O O

O

has two single bonds and one double bond.
The structure is easier to see if we write it as a
mixed Lewis/Kekul structure, with each bonding
electron pair represented by a single line.
It has three possible resonance structures.
The hybrid is the full set of resonance structures.
Locate the charges in each of the resonance structures.
What is the charge distribution in the actual molecule?
Models and Representations
An aside.
 We have now seen two different structures
both said to represent ethene:

H C C H HC CH
H H H H
...and saw too that we needed to use three
different structures, each representing the
carbonate ion, somehow mixed together, to
represent the real structure of the ion.

Obviously none of these models

exactly represents the thing itself.
 Obviously none of these models
exactly represents the thing itself.
No model can.
Every model is designed to illustrate best particular
aspects of the thing that it represents.
- each has its own conventions for use and interpretation.
- and for each, there are aspects that it does not indicate.
Therefore...
You must learn the conventions of each model
that you use, or you will make errors using it.
The same point made
another way

Le Condition Humaine Ren Magritte

 More Resonance
Structures to Build
Practice, practice, practice...
Problem 1-6
Draw the full set of resonance structures
and assign formal charges for:

NO3-

CO

CH3C(OH)CH3+
Lewis structures have
problems of their own:
exceptions to the octet rule.
Fewer than 8 electrons (BF3)
An odd number of electrons (NO)
More than 8 electrons (PCl5)
Fewer than 8 electrons: BF3

FBF The structure indicates that

there are only six electrons
around the boron atom.
F

BF3 is stable, but it is reactive.

 BF3

H

FBF NH

F H

For example, BF3 can react with the

unshared electron pair of ammonia.
Draw the resulting molecule.
Assign formal charges.
An odd number of
electrons
NO : 5 + 6 = 11 valence electrons
There is no way to pair 11 electrons
to get a perfect Lewis structure.
This leaves us with only a
couple of good options:

N=O But both are problematic

They are also resonance states.

N=O Does either resonance state have

formal charges? If so, assign them.
More than 8 electrons
PCl5
Electrons of atoms from the 3rd row or greater can
expand into vacant d orbitals.
(Second row atoms do not have available d orbitals.)
The result is an expanded valence shell (on
phosphorous, in this case).
Cl Cl
Cl P Cl

Cl
Problem 1-7

Draw Lewis structures for the following.

a) ICl4
b) SF6
c) XeF6