Organic Chemistry

Introduction and Brief History

Definition
Organic Chemistry
Study of compounds containing carbon

Organic Compounds
Covalent bond
Mostly nonpolar
Low melting point
Low conductivity
Flammable with black residue
Complex structure
Inorganic Compounds
Ionic bond
Mostly polar
High melting point
High conductivity
Non-flammable
Simple structure
Why is carbon so special?
It can form four
bonds

It can form stable
single, double and
triple bonds

It can form stable
C-C bond
catenation
Brief History
Pre-1700s
Compounds derived from living things are
organic
Compounds derived from non-living things are
inorganic
Vitalism Theory

1828
Friedlich Whler synthesized urea from
ammonium cyanate

1890
August Kekule proposed the structure of
benzene
Established the foundation of structural biochemistry
ATOMIC STRUCTURE
AND CHEMICAL
BONDING
Review
Quantum Mechanical Model
1926
Erwin Schrdinger,
Werner Heisenberg
and Paul Dirac
Motion of electrons
described as wave
functions ()
Energy
Relative probability of
the position
Atomic Orbitals
An orbital is a region in space where the
probability of finding an electron is high
Orbitals of equal energy are degenerate
orbitals

Electronic Configuration
Aufbau Principle
Building up
Orbitals are filled so that those with lower
energies are filled first

Pauli Exclusion Principle
A maximum of two electrons with opposite spins
can occupy an orbital

Hunds Rule
For degenerate orbitals, one electron with
unpaired spin is added until all degenerate
orbitals are filled before adding the second
electron
Example
Draw the electron configurations of:

C
0

O
0

O
-2

F
-1

H
-2

N
0

N
-3

Chemical Bonding
Ionic Bond




Covalent Bond
Theories of Chemical Bonding
Valence Bond Theory
Covalent bond forms from overlapping
atomic orbitals

Molecular Orbital Theory
Molecular orbitals are formed from the
arithmetic sum of atomic orbitals
Valence Bond Theory
A covalent bond forms
when two atoms
approach each other
closely and a singly-
occupied obital on one
atom overlaps with a
singly-occupied orbital on
another atom

Bond length
Distance between the
nuclei of the two atoms

Bond energy
The lower the bond
energy, the more stable
the bond
Valence Bond Theory
Sigma bond
()
Bond formed by
a head-on
overlap of two
orbitals

Can occur
between:
s-s orbitals
s-p orbitals
p-p orbitals


Valence Bond Theory
Orbital Hybridization
sp
3
Hybrid Orbitals
sp
3
Hybridization: Methane
sp
3
Hybridization: Ethane
sp
3
Hybridization of other
atoms
sp
2
Hybrid Orbitals
Pi Bond ()
Formed by
sideways
overlap of two
parallel p
orbitals
Occurs between
p-p orbitals

sp
2
Hybridization: Ethylene
sp Hybrid Orbitals
sp Hybridization: Acetylene
Hybridization: Summary
Hybrid
Orbitals
Total
Bonds
C-C Bond
Length
C-H Bond
Angle
C-C Bond
Strength
Geometry
of C
sp
3
1 () 154 pm
111.2
376 kJ/mol Tetrahedra
l
sp
2
2 (+) 134 pm
121.3
728 kJ/mol Planar
sp 3 (+2) 120 pm
180
556 kJ/mol Linear
Activity
Identify the hybridization of the atoms
(except H) for each of the following
Limitations of VB Theory
Fails in predicting magnetic properties
of compounds (especially in O
2
)

Cannot fully explain the behavior of
benzene and other conjugated
compounds
Molecular Orbital Theory
A covalent bond forms from the mathematical
combination of wave functions (orbitals) of atoms to
form molecular orbitals

Total AO combined = MO formed
Molecular Orbital Theory
REVIEW: LEWIS
STRUCTURES AND
FORMAL CHARGE
31
1. Draw skeletal structure of compound showing
what atoms are bonded to each other. Put
least electronegative element in the center.
2. Count total number of valence e

. Add 1 for
each negative charge. Subtract 1 for each
positive charge.
3. Draw a single covalent bond between the
central and each surrounding atom. Complete
an octet for all atoms except hydrogen,
beginning with the surrounding atoms.
4. If central atom has fewer than eight electrons,
form double and triple bonds on central atom
as needed.
Writing Lewis Structures
Examples
Water
Ammonia
Methanol (CH
3
OH)
Methyl chloride (CH
3
Cl)
Propene (CH
2
CHCH
3
)
Propyne (CH
3
CCH)
33
Two possible skeletal structures of formaldehyde (CH
2
O)
H C O H
H
C O
H
An atoms formal charge is the difference between the
number of valence electrons in an isolated atom and the
number of electrons assigned to that atom in a Lewis
structure.
formal charge
on an atom in
a Lewis
structure
=
1
2
total number
of bonding
electrons
( )
total number
of valence
electrons in
the free atom
-
total number
of nonbonding
electrons
-
The sum of the formal charges of the atoms in a molecule
or ion must equal the charge on the molecule or ion.
34
H C O H
C 4 e
-

O 6 e
-

2H 2x1 e
-

12 e
-

2 single bonds (2x2) = 4
1 double bond = 4
2 lone pairs (2x2) = 4
Total = 12
formal charge
on C
= 4 - 2 - x 6 = -1
formal charge
on O
= 6 - 2 - x 6 = +1
formal charge
on an atom in
a Lewis
structure
=
1
2
total number
of bonding
electrons
( )
total number
of valence
electrons in
the free atom
-
total number
of nonbonding
electrons
-
-1 +1
35
C 4 e
-

O 6 e
-

2H 2x1 e
-

12 e
-

2 single bonds (2x2) = 4
1 double bond = 4
2 lone pairs (2x2) = 4
Total = 12
H
C O
H
formal charge
on C
= 4 - 0 - x 8 = 0
formal charge
on O
= 6 - 4 - x 4 = 0
formal charge
on an atom in
a Lewis
structure
=
1
2
total number
of bonding
electrons
( )
total number
of valence
electrons in
the free atom
-
total number
of nonbonding
electrons
-
0 0
Examples
Calculate the formal charges of non-
hydrogen atoms

Diazomethane (CH
2
NN)
Acetonitrile oxide (CH
3
CNO)
Methyl isocyanide (CH
3
NC)
Resonance Structures
Consider the Lewis structure of
carbonate




What would you expect from the
lengths of each of the C-O bonds?
Resonance Structures
X-ray data of the C-O bond in carbonate shows that all
three have the same length







Resonance Theory
Whenever the molecule or ion can be represented by two
or more Lewis structures differing only in the position of
electrons, then:
None of these structures (resonance contributors) is the actual
representation of the molecule
The actual structure is a hybrid of the structures

Rules of Resonance
Resonance structures exists only on paper
In writing resonance structures, only electrons are allowed
to move
All structures must be proper Lewis structures
The energy of the actual molecule is lower than the
energy that might be estimated from the contributing
structure
Equivalent resonance structures make equal contributions
to the hybrid and a system described by them has a large
resonance stabilization
The more stable a resonance structure is, the greater its
contribution to the hybrid
The more covalent bond a structure is, the more stable it is
Structures in which all of the atoms have a complete valence
shell of electrons are especially stable
Charge separation decreases stability
Resonance contributors with negative charge on highly
electronegative atoms are more stable
Examples