molecule because it prevents one part of a molecule from rotating relative to
another part. The double bond of ethene, for example, holds the entire molecule
flat. Figure 4.19 shows that the two 2p-orbitals overlap best if all six atoms of the
two CH2 groups lie in the same plane. In order for the molecule to rotate about the
double bond, the -bond would need to break and re-form.
Double bonds and their influence on molecular shape are vitally important for
living organisms. For instance, they enable you to read these words. Vision depends
on the shape of the molecule retinal in the retina of the eye. cis-Retinal is held rigid
by its double bonds (41). When light enters the eye, it excites an electron out of the
-bond marked by the arrow. The double bond is now weaker, and the molecule is
free to rotate about the remaining -bond. When the excited electron falls back, the
molecule has rotated about the double bond and is now trapped in its trans shape
(42). This change in shape triggers a signal along the optic nerve and is interpreted
by the brain as the sensation of vision.
Now consider the alkynes, hydrocarbons with carbon–carbon triple bonds.
The Lewis structure of the linear molecule ethyne (acetylene) is HßCΩCßH. A
linear molecule has two equivalent orbitals at 180 from each other: this is sp
hybridization. Each C atom has one electron in each of its two sp hybrid orbitals
and one electron in each of its two perpendicular unhybridized 2p-orbitals (43).
The electrons in one of the sp hybrid orbitals on each carbon atom pair and form
a carbon–carbon -bond. The electrons in the two remaining sp hybrid orbitals
pair with hydrogen 1s-electrons to form two carbon–hydrogen -bonds. The electrons
in the two perpendicular sets of 2p-orbitals pair with a side-by-side overlap,
forming two -bonds at 90 to each other. As in the N2 molecule, the electron density
in the -bonds forms a cylinder about the C¬C bond axis. The resulting bonding
pattern is shown in FIG. 4.23.
THINKING POINT What shape do the atoms connected to two triply bonded carbon
atoms impose on a molecule that contains such a group?
We can now understand why a carbon–carbon double bond is stronger than
one carbon–carbon single bond but weaker than the sum of two single bonds (Section
3.15), and why a carbon–carbon triple bond is weaker than the sum of three
carbon–carbon single bonds. Recall that a single CßC bond is a -bond, but the
additional bonds in a multiple bond are -bonds. One reason for the difference in
strength is that because the p-orbitals overlap in a side-by-side fashion, the overlap
in a -bond is smaller and weaker than the end-to-end overlap that results in a
-bond. The side-by-side overlap also explains why double bonds are rarely formed
between elements in periods later than Period 3. The atoms are too large for the
overlap to be strong enough to form a bond.