Organic Chemistry

Janice Gorzynski Smith

Chapter 1

Structure and Bonding

A periodic table of the common elements seen in organic chemistry

2
 Overview of Concepts

• Structural theory
• Drawing organic molecules
• Molecular shape
• Electronic descriptions of organic molecules
o Lewis structures
o bond and molecule polarity
o hybrid orbitals and bonding
o resonance theory

Review of Bonding

• Bonding is the joining of two atoms in a stable arrangement.

• Through bonding, atoms attain a complete outer shell of valence
electrons.
electrons
• Through bonding, atoms attain a stable noble gas configuration.
• Ionic bonds result from the transfer of electrons from one element to
another.
• Covalent bonds result from the sharing of electrons between two nuclei.

4
 Structural Theory

Central Premises
• Valency: atoms in organic compounds form a fixed number
of bonds

• Carbon can form one or more bonds to other carbons

• Three Dimensional Shape of Molecules

• Virtually all molecules possess a 3-dimensional shape which is
often not accurately represented by drawings
• It was proposed in 1874 by van
van’tt Hoff and le Bel that the four bonds
around carbon where not all in a plane but rather in a tetrahedral
arrangement, i. e. the four C-H bonds point towards the corners of a
regular tetrahedron

6
 Isomers

• Isomers are different molecules with the same molecular formula

• Many types of isomers exist
• Example
p
– Consider two compounds with molecular formula C2H6O
– These compounds cannot be distinguished based on
molecular formula; however they have different structures
– The two compounds differ in the connectivity of their atoms

Constitutional Isomers

• Constitutional isomers are one type of isomer

• They are different compounds that have the same molecular
formula but different connectivity
y of atoms
• They often differ in physical properties (e.g. boiling point, melting
point, density) and chemical properties

8
 Condensed Structures
• All atoms are drawn in, but the two-electron bond lines are generally
omitted.
• Atoms are usually drawn next to the atoms to which they are
b d d
bonded.
• Parentheses are used around similar groups bonded to the same
atom.
• Lone pairs are omitted.

Skeletal Structures

• Assume there is a carbon atom at the junction of any two

lines or at the end of any line.
• Assume there are enough hydrogens around each carbon to
make it tetravalent.
• Draw in all heteroatoms and hydrogens directly bonded to
them.
them

10
 Skeletal Structures

11

Molecular Shape

Two variables define a molecule’s structure: bond length

and bond angle.
• B
Bondd length
l th decreases
d across a row off the
th periodic
i di
table as the size of the atom decreases.

• Bond length increases down a column of the

periodic table as the size of an atom increases.

12
 Bond Length

13

Bond Length and Strength

• As the number of electrons between two nuclei

increases, bonds become shorter and stronger.
• Thus, triple bonds are shorter and stronger than
double bonds, which are shorter and stronger than
single
i l bonds.
b d

14
 Bond Length and Strength

15

Bond Angle

Bond angle determines the shape around any atom

bonded to two other atoms.
• The number of groups surrounding a particular atom
determines its geometry. A group is either an atom or a
lone pair of electrons.
• The most stable arrangement keeps these groups as
far away from each other as possible. This is
exemplified by Valence Shell Electron Pair Repulsion
(VSEPR) theory.

16
 Bond Angle

Two groups around an atom—

17

Bond Angle

Th
Three groups around
d an atom—
t

18
 Bond Angle

Four groups around an atom—

19

Drawing Three Dimensional Structures

• A solid line is used for a bond in the plane.

• A wedge is used for a bond in front of the plane.
plane
• A dashed line is used for a bond behind the plane.

20
 Drawing Three Dimensional Structures

A Nonbonded Pair of Electrons is Counted as a

“Group”
Group
In ammonia (NH3), one of the four groups attached to the
central N atom is a lone pair. The H-N-H bond angle of
107° is close to the theoretical tetrahedral bond angle of
109.5°. This shape is referred to as a trigonal pyramid.

21

Drawing Three Dimensional Structures

In water (H2O),
O) two of the four groups attached to the
central O atom are lone pairs. The H-O-H bond angle
of 105° is close to the theoretical tetrahedral bond
angle 109 5°. Water
l off 109.5 W t has
h a bent
b t shape,
h b
because th
the
two groups around oxygen are lone pairs of electrons.

22
 Lewis Structures
General rules :
1. Draw only the valence electrons.
2 Let every second
2. second-row
row element share an octet of
electrons, if possible.
3. Let each hydrogen
y g share two electrons.

23

Formal Charge

• Formal charge is the charge assigned to individual atoms in a

Lewis structure.
• Formal charge is calculated as follows:

• The number of electrons “owned” by an atom is determined

by its number of bonds and lone pairs.
• An atom “owns” all of its unshared electrons and half of its
shared electrons.

24
 Formal Charge

25

Electronegativity and Bond Polarity

Electronegativity is a measure of an atom’s attraction for

electrons in a bond.
Electronegativity values for some common elements:

26
 Electronegativity and Bond Polarity
Electronegativity
ect o egat ty values
a ues a
are
e used as a gu
guideline
de e to indicate
d cate whether
et e
the electrons in a bond are equally shared or unequally shared
between two atoms. When electrons are equally shared, the bond is
nonpolar. When differences in electronegativity result in unequal
sharing of electrons, the bond is polar, and is said to have a
“separation of charge” or a “dipole”.

• A carbon—carbon bond is nonpolar. The same is true whenever

two different atoms having similar electronegativities are bonded
together.
g
• C—H bonds are considered to be nonpolar because the
27
electronegativity difference between C and H is small.

Electronegativity and Bond Polarity

Bonding
o d g bet
between
ee ato
atoms soof d
different
e e teelectronegativity
ect o egat ty values
a ues results
esu ts in
unequal sharing of electrons.
In the C—O bond, the electrons are pulled away from C (2.5) toward O
(3 4) the element of higher electronegativity.
(3.4), electronegativity The bond is polar,
polar or
polar covalent. The bond is said to have dipole; that is, separation of
charge.
δ+ means the
th
indicated atom is
electron deficient.
δ- means the
indicated atom is
electron rich.
The direction of polarity in a bond is indicated by an arrow with the
head of the arrow pointing towards the more electronegative element.
The tail of the arrow,, with a p
perpendicular
p line drawn through
g it,, is
drawn at the less electronegative element.
28
 Polarity of Molecules
A polar molecule has either one polar bond, or two or more
bond dipoles that reinforce each other. An example is water:

10

A nonpolar molecule has either no polar bonds, or two or

more bond dipoles that cancel. An example is carbon dioxide:

11

29

Orbitals and Bonding

When the 1s orbital of one H atom overlaps with the 1s

orbital of another H atom, a sigma (σ) bond that
concentrates electron density between the two nuclei is
formed.
This bond is cylindrically symmetrical because the
electrons forming the bond are distributed symmetrically
about an imaginary line connecting the two nuclei.

30
 sp3 Hybrid Orbitals

The mixing of a spherical 2s orbital and three dumbbell

shaped 2p orbitals together produces four hybrid orbitals,
each having
g one large
g lobe and one small lobe

The four hybrid orbitals are oriented towards the corners of a

tetrahedron, and form four equivalent bonds.

31

Bonding Using sp3 Hybrid Orbitals

Each bond in CH4 is formed by overlap of an sp3 hybrid

orbital of carbon with a 1s orbital of hydrogen.
y g These
four bonds point to the corners of a tetrahedron.

32
 Bonding Using sp3 Hybrid Orbitals

33

Bonding Using sp3 Hybrid Orbitals

Rotation occurs around the central C C σ bond in

C—C
ethane.

34
 sp2 Hybrid Orbitals

35

Bonding Using sp2 Hybrid Orbitals

Unlike the C—C bond in ethane,, rotation about the C—C

double bond in ethylene is restricted. It can only occur if the π
bond first breaks and then reforms, a process that requires
considerable energy.
gy

36
 sp Hybrid Orbitals

Each carbon atom has two

unhybridized 2p orbitals that
are perpendicular to each
other and to the sp hybrid
orbitals. The side-by-side
overlap of two 2p orbitals on
one carbon with two 2p
orbitals on the other carbon
creates the second and third
bonds of the triple bond.
bond All
triple bonds are composed of
37
one sigma and two pi bonds.

Bonding Using sp Hybrid Orbitals

38
Summary of Covalent Bonding in Carbon Compounds

39

Resonance Theory

Some molecules cannot be adequately represented by a single

Lewis structure. For example, two valid Lewis structures can be
drawn for HCONH2:

12

These structures are called resonance structures or resonance

forms. A double headed arrow is used to separate the two
resonance structures.
t t

40
 Resonance Theory

• Neither resonance structure is an accurate representation

for HCONH2. The true structure is a composite of both
resonance forms and is called a resonance hybrid.
• The hybrid
y shows characteristics of both structures.
• Resonance allows certain electron pairs to be delocalized
over two or more atoms, and this delocalization adds
stability.
stability
• A molecule with two or more resonance forms is said to be
resonance stabilized.

41

Resonance Theory

The following basic principles of resonance theory should

be kept in mind:

1. Resonance structures are not real. An individual

resonance structure does not accurately represent the
structure of a molecule or ion. Only the hybrid does.
2. Resonance structures are not in equilibrium with each
other. There is no movement of electrons from one form
to another.
3. Resonance structures are not isomers. Two isomers
diff in
differ i the
th arrangementt off both
b th atoms
t and
d electrons,
l t
whereas resonance structures differ only in the
arrangement of electrons.

42
 Drawing Resonance Structures
Rule
R l [1]:
[1] Two
T resonance structures
t t diff in
differ i the
th position
iti off multiple
lti l
bonds and nonbonded electrons. The placement of atoms and single
bonds always stays the same.

Rule [2]: Two resonance structures must have the same number of
unpaired electrons.

43

Drawing Resonance Structures

Rule [[3]:
] Resonance structures must be valid Lewis structures.
Hydrogen must have two electrons and no second-row element can
have more than eight.

44
 Drawing Resonance Structures

• Curved arrow notation is a convention that is used to show how

electron position differs between the two resonance forms.
• Curved arrow notation shows the movement of an electron pair.
The tail of the arrow always begins at the electron pair, either in a
bond or lone pair. The head points to where the electron pair
“moves.”

13

14
45

Resonance Hybrids

• A resonance hybrid is a composite of all possible

resonance structures. In the resonance hybrid, the
electron pairs drawn in different locations in individual
resonance forms are delocalized.
• When two resonance structures are different, the
hybrid looks more like the “better” resonance
structure. The “better” resonance structure is called
the major contributor
contrib tor to the hybrid,
h brid and all others are
minor contributors.
• The hybrid is a weighted average of the contributing
resonance structures.

46
 Rules to Assign Relative Importance of
Resonance Forms
• A resonance form with more covalent bonds is more important than one
with less:
– 6 is more stable and more important because it has more total covalent bonds

• Resonance forms in which all atoms have a complete valence shell of

electrons are more important:
– 10 is more important because all atoms (except hydrogen) have complete
octets

47

• Resonance forms with separation of charge are less important

– S
Separation
ti off charge
h costt energy and
d results
lt in
i a less
l stable
t bl resonance
contributor
– 12 is less important because it has charge separation

• Forms with negative charge on highly electronegative atoms are

more important
– Those with positive charge on less electronegative atoms are also more
important

48