Conformation & Conformational Isomers

What is Conformation?
In alkanes, the distribution of electrons in sigma molecular orbital is symmetrical
around the internuclear axis of the C-C bond. Thus, it permits the possibility of free
rotation about the C-C single bond. Due to this rotation, different spatial arrangements
of carbon atoms in space are observed which can change into one another. Such spatial
arrangement of carbon, hydrogen atoms which can be converted into one another by
rotation around a C-C single bond is called confirmation or conformer or rotamer.
Alkanes can thus have an infinite number of conformations by rotation around C-C
single bonds. However, this rotation is not completely free due to repulsive interactions
between the electron clouds of C-H bonds. This repulsive interaction is termed as
torsional strain.
Conformational Isomers
Let us understand the fundamentals of conformation with the example of ethane. If we
observe the ball and stick model of ethane and rotate one carbon atom keeping another
carbon atom stationary about C-C axis. We will observe that the rotations will result in
an infinite number of spatial arrangements of hydrogen atoms attached to one carbon
atom with respect to the hydrogen atoms attached to the other carbon atom. These
different arrangements are better known as conformational isomers or conformers.
Predominantly, these can be broadly classified into two different cases:
1. Eclipse conformation
Conformation in which hydrogen atoms attached to two carbons areas nearest to
each other as possible is known as eclipsed
2. Staggered conformation
Conformation in which hydrogen atoms attached to two carbons are as far as
possible with respect to each other is known as staggered The staggered
conformation is thus relatively more stable in comparison to eclipse conformation as
there are minimum repulsive forces, minimum energy due to much separation
between the electron clouds of C-H bonds.
Representation of Eclipsed and Staggered Conformation:
Sawhorse projections:
In this kind of projection, the bond between carbon atoms is shown as a long straight
line. The lower end of the line designates the front carbon atom whereas the upper end
designates the rear carbon atom. Since each carbon atom in ethane is attached to three
hydrogen atoms; each carbon atom has three lines attached designating C-H bonds
inclined at an angle of 120° to each other.
Newman projections:
In this projection, out of the two carbon atoms present in ethane one which is nearer is
shown as a dot whereas the rear carbon atom is represented as a circle. The three
hydrogen atoms
s attached to each carbon atom are represented with the help of three
lines either bulging out of the circle or diverging of the dotted lines. These lines are
inclined to each other at an angle of 120° to each other.

So, Rotation about the C-C bond in ethane produces different conformation
conformations. Although
an infinite number of conformations are possible,
the staggered and eclipsed conformations which represent the most and least stable
respectively are the two most important.
The staggered conformation is the most stable conformation for ethane since
the torsional strain is minimised. The staggered conformation is 12kJ/mol (2.9
kcal/mol) more stable than the eclipsed conformation.
Butane: CH3-CH2-CH2-CH3

In butane it is the rotation about the C2-C3 bond that is of most interest since the
relative position of the two methyl groups is important.
This can be seen most easily by rotating the molecule to view it down the C2-C3bond.
ANTI
a staggered conformation with the Me groups at 180o with respect to each other. This is
the most stable conformation since the Me groups are as far apart as possible.

GAUCHE
a staggered conformation with the Me groups at 60o with respect to each other.

SYN
an eclipsed conformation with the Me groups at 0o with respect to each other. This is the
least stable conformation due to the steric strain caused by the proximity of the Me
groups and the torsional strain of the eclipsed bonds.

GAUCHE
a staggered conformation with the Me groups at 60o with respect to each other
Cyclohexane

A cyclohexane conformation is any of several three-dimensional shapes that

The internal angles of a flat regular hexagon are 120°, while the preferred angle between
successive bonds in a carbon chain is about 109.5°, the tetrahedral angle. Therefore, the
cyclohexane ring tends to assume certain non-planar (warped) conformations, which
have all angles closer to 109.5° and therefore a lower strain energy than the flat
hexagonal shape. The most important shapes are called chair, half-chair, boat,
and twist-boat. The molecule can easily switch between these conformations, and only
two of them—chairand twist-boat—can be isolated in pure form.

The most stable conformation of cyclohexane is the chair form shown to the right.
The C-C-C bonds are very close to 109.5o, so it is almost free of angle strain. It is also a
fully staggered conformation and so is free of torsional strain.
In chair cyclohexane there are two types of positions, axial and equatorial.
The axialpositions point perpendicular to the plane of the ring, whereas
the equatorial positions are around the plane of the ring.

Conformational Energy Profile of Cyclohexane

TC = twist chair B = boat TB = twist boat C = chair