Conformational Analysis of Butane

If we consider rotation about the C2 C3 bond of butane, we find that there are s
ix important
conformers, shown as IVI below
The anti conformation (I) does not have torsional strain from steric hindrance b
ecause
the groups are staggered and the methyl groups are far apart. The anti conformat
ion is the
most stable. The methyl groups in the gauche conformations III and V are close e
nough
to each other that the dispersion forces between them are repulsive; the electro
n clouds of
the two groups are so close that they repel each other. This repulsion causes th
e gauche conformations
to have approximately 3.8 kJ mol1 more energy than the anti conformation.
The eclipsed conformations (II, IV, and VI) represent energy maxima in the poten
tial
energy diagram (Fig. 4.8). Eclipsed conformations II and VI have repulsive dispe
rsion
forces arising from the eclipsed methyl groups and hydrogen atoms. Eclipsed conf
ormation
IV has the greatest energy of all because of the added large repulsive dispersio
n forces
between the eclipsed methyl groups as compared to II and VI.
Although the barriers to rotation in a butane molecule are larger than those of
an ethane
molecule (Section 4.8), they are still far too small to permit isolation of the
gauche and anti
conformations at normal temperatures. Only at extremely low temperatures would t
he
molecules have insufficient energies to surmount these barriers.
I
An anti
conformation
III
A gauche
conformation
V
A gauche
conformation
VI
An eclipsed
conformation
II
An eclipsed
conformation
H
H
H
CH3
CH3 H
H H
CH H 3 CH3
H
H H
H
CH3
CH3 H
H H
H
CH3
CHH 3
CHH 3
H H
HCH3
IV
An eclipsed
conformation
H H
H H
CH3 H3C
9
4.9 Conformational Analysis of Butane 161
Rotation
Potential energy
CH3 CH3
CH3
H3C CH3
H3C
H H
H
H
H
H
H3C CH3
H H
CH3
CH3
H
H
H
H
H H
H H
CH3
CH3
H H
H H
H
H
H
H
CH3
CH3
H H
H H
Eclipsed II Eclipsed VI
Eclipsed IV
Anti I Gauche III Gauche V Anti I
0 60 120 180 240 300 360
16 kJ mol1 16 kJ mol1
19 kJ mol1
3.8 kJ mol1 3.8 kJ mol1
Figure 4.8 Energy changes
that arise from rotation about
the C29C3 bond of butane.
We saw earlier (Section 2.16C) that dispersion forces can be attractive. Here, h
owever,
we find that they can also be repulsive, leading to steric hindrance. Whether
dispersion interactions lead to attraction or to repulsion depends on the distan
ce
that separates the two groups. As two nonpolar groups are brought closer and
closer together, the first effect is one in which a momentarily unsymmetrical
distribution of electrons in one group induces an opposite polarity in the other
.
The opposite charges induced in those portions of the two groups that are in clo
sest
proximity lead to attraction between them. This attraction increases to a maximu
m
as the internuclear distance of the two groups decreases. The internuclear dista
nce
at which the attractive force is at a maximum is equal to the sum of what are ca
lled
the van der Waals radii of the two groups. The van der Waals radius of a group i
s,
in effect, a measure of its size. If the two groups are brought still closerclose
r
than the sum of their van der Waals radiithe interaction between them becomes
repulsive. Their electron clouds begin to penetrate each other, and strong
electronelectron interactions begin to occur.