Lecture 1.
Part 2:
ORBITAL PICTURE OF
BONDING:
ORBITAL COMBINATIONS,
HYBRIDIZATION THEORY, &
MOLECULAR ORBITALS
Organic Chemistry 1
Hybridization
the concept of mixing atomic orbitals
to form new hybrid orbitals suitable
for the qualitative description of
atomic bonding properties
ORBITAL HYBRIDIZATION
THEORY
If we look at the valence shell configuration of carbon, we find
two paired electrons in the 2s orbital, and two unpaired
electrons in the 2pX and 2pY orbitals, one in each:
Two paired electrons occupying the 2s orbital must become
unpaired before they can bond. Since the energy gap between
the 2s and 2p orbitals is very small, one of the 2s electrons can be
promoted to the empty 2p orbital, leading to the following
situation:
The shapes and relative positions of the valence
orbitals in atomic carbon do not explain the shapes
and relative positions of the bonds in carbon
compounds.
The first step is to take either 2, 3, or all four of those
orbitals and equalize their energies. Let’s say that we take
all four of them and form 4 equivalent new orbitals. These
orbitals are now of the same energy, which is intermediate
between those of the original 2s and 2p orbitals. At the
same time, we cannot name the new orbitals s or p. We
have to find a new name that reflects the fact that they
were created from one s orbital and three p orbitals. We
will call them sp3 orbitals. The process that leads to their
formation is called sp3 hybridization.
ORBITAL HYBRIDIZATION
THEORY
HYDROCARBONS
Hydrocarbons are substances containing only
carbon and hydrogen. Hydrocarbons are
classified into the following major categories:
alkanes, alkenes, alkynes, and aromatic
hydrocarbons.
SIGMA BONDING
When orbitals approach each other in a head to head
fashion, the resulting covalent bonds are called sigma
bonds.
LINE-ANGLE FORMULAS
ALKENES AND sp2
HYBRIDIZATION OF CARBON
We’ll take only one s and two p orbitals to make three
equivalent sp2 orbitals, leaving one p orbital untouched.
The process is shown below.
The three equivalent sp2 orbitals will arrange
themselves in a trigonal planar configuration.
That is to say, the carbon nucleus will be at the
center of an equilateral triangle, and the three
sp2 orbitals will point to the corners of that
triangle. The ideal angle between sp2 orbitals
is therefore 120o . A top view:
ALKENES AND sp2
HYBRIDIZATION OF CARBON
side view of the orbital system
When two sp2 hybridized carbon atoms approach each
other to bond, two sp2 orbitals approach each other
head to head, and two p orbitals approach each other
sideways. The bond formed by the sp2 orbitals is a
sigma bond, and the bond formed by the p orbitals is
called a pi bond.
The sigma bond is short and strong. As a rule, head
to head overlap is the most efficient way to bond and
results in relatively strong and stable bonds. The pi
bond, on the other hand, is relatively long and diffuse.
Sideways overlap is less efficient than head to head
overlap and results in formation of weaker bonds.
The electrons in the sigma bond (or sigma electrons)
are more tightly bound to the nucleus and don’t move
too much. In other words, they are more LOCALIZED.
The electrons in the pi bond (or pi electrons) are less
tightly bound by the nucleus, and therefore they are
relatively mobile. Under certain conditions, they have
the capability to become DELOCALIZED, that is to say,
they can move in the molecular skeleton from one
atom to another, or even become spread over several
atoms.
In chemical reactions where electrons are to be traded,
the pi electrons are more readily available because
they are more exposed and less tightly bound by the
nucleus.
ALKYNES AND sp
HYBRIDIZATION OF CARBON
sp hybridization gives rise to the formation of hydrocarbons
known as alkynes. Alkynes contain at least one triple bond,
and have linear geometry around the carbons comprising the
triple bond. Therefore, the ideal angle between the sp hybrid
orbitals is 180o. Some examples of alkynes are shown below.
Practice
Practice
Practice
Practice
Practice
