13.2.4 Conformations

Alkanes contain carbon-carbon sigma (σ) bonds. Electron distribution of the sigma molecular orbital is symmetrical around the internuclear axis of the C–C bond which is not disturbed due to rotation about its axis. This permits free rotation about C–C single bond.

This rotation results into different spatial arrangements of atoms in space which can change into one another. Such spatial arrangements of atoms which can be converted into one another by rotation around a C-C single bond are called conformations or conformers or rotamers. Alkanes can thus have infinite number of conformations by rotation around C-C single bonds.

However, it may be remembered that rotation around a C-C single bond is not completely free. It is hindered by a small energy barrier of 1-20 kJ mol–1 due to weak repulsive interaction between the adjacent bonds. Such a type of repulsive interaction is called torsional strain. Conformations of ethane : Ethane molecule contains a carbon – carbon single bond with each carbon atom attached to three hydrogen atoms.

Considering the ball and stick model of ethane, keep one carbon atom stationary and rotate the other carbon atom around the C-C axis. This rotation results into 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 are called conformational isomers (conformers).

Thus there are infinite number of conformations of ethane. However, there are two extreme cases. One such conformation in which hydrogen atoms attached to two carbons are as closed together as possible is called eclipsed conformation and the other in which hydrogens are as far apart as possible is known as the staggered conformation.

Any other intermediate conformation is called a skew conformation.It may be remembered that in all the conformations, the bond angles and the bond lengths remain the same. Eclipsed and the staggered conformations can be represented by Sawhorse and Newman projections.

1. Sawhorse projections

In this projection, the molecule is viewed along the molecular axis. It is then projected on paper by drawing the central C–C bond as a somewhat longer straight line.

Upper end of the line is slightly tilted towards right or left hand side. The front carbon is shown at the lower end of the line, whereas the rear carbon is shown at the upper end. Each carbon has three lines attached to it corresponding to three hydrogen atoms.

The lines are inclined at an angle of 120° to each other. Sawhorse projections of eclipsed and staggered conformations of ethane are depicted in Figure.

2. Newman projections

In this projection, the molecule is viewed at the C–C bond head on. The carbon atom nearer to the eye is represented by a point. Three hydrogen atoms attached to the front carbon atom are shown by three lines drawn at an angle of 120° to each other.

The rear carbon atom (the carbon atom away from the eye) is represented by a circle and the three hydrogen atoms are shown attached to it by the shorter lines drawn at an angle of 120° to each other. The Newman’s projections are depicted in Figure.

Relative stability of conformations: As mentioned earlier, in staggered form of ethane, the electron clouds of carbon-hydrogen bonds are as far apart as possible.

Thus, there are minimum repulsive forces, minimum energy and maximum stability of the molecule. On the other hand, when the staggered form changes into the eclipsed form, the electron clouds of the carbon – hydrogen bonds come closer to each other resulting in increase in electron cloud repulsions.

To check the increased repulsive forces, molecule will have to possess more energy and thus has lesser stability. As already mentioned, the repulsive interaction between the electron clouds, which affects stability of a conformation, is called torsional strain.

Magnitude of torsional strain depends upon the angle of rotation about C–C bond. This angle is also called dihedral angle or torsional angle. Of all the conformations of ethane, the staggered form has the least torsional strain and the eclipsed form, the maximum torsional strain.

Therefore, staggered conformation is more stable than the eclipsed conformation. Hence, molecule largely remains in staggered conformation or we can say that it is preferred conformation. Thus it may be inferred that rotation around C–C bond in ethane is not completely free.

The energy difference between the two extreme forms is of the order of 12.5 kJ mol–1, which is very small. Even at ordinary temperatures, the ethane molecule gains thermal or kinetic energy sufficient enough to overcome this energy barrier of 12.5 kJ mol–1 through intermolecular collisions.

Thus, it can be said that rotation about carbon-carbon single bond in ethane is almost free for all practical purposes. It has not been possible to separate and isolate different conformational isomers of ethane.

 

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