Conformations of Ethane -Introduction to Conformational Analysis

by ;- kanha

In the last chapter, we saw that it was possible to describe the complete 3-dimensional shape of methane by specifying its bond angles and bond lengths. Ethane, which is comprised of two methyl groups attached to each other, has properties very similar to those of methane. However, the complete 3-dimensional shape of ethane cannot be specified by these bond lengths and bond angles alone because ethane can internally rotate about its C-C bond. To understand why ethane has this extra degree of freedom, consider the cylindrically symmetric nature of $\sigma$ bonds. The $\sigma$ bond can maintain a full degree of overlap while its two ends rotate. Hence, the energetic barrier to rotation about sigma bonds is generally very low. Unlike $\pi$ bonds in alkenes, the C-C sigma bond does not hold the two methyl groups in fixed positions relative to one another. The different spatial arrangements formed by rotations about a single bond are called conformations or conformers.

Figure %: Free rotation about the C-C $\sigma$ bond in ethane.

Visualizing Conformations Several methods are used by organic chemists to help them visualize the conformations of molecules. One of these methods uses wedges to denote bonds that are extending out from the plane of the page toward the reader and dashes to indicate bonds that are going into the plane of the page away from the reader. This notation is frequently used to represent the tetrahedral geometry of $sp^3$-hydridized carbons. A Newman projection can be used to specify the conformation of a particular bond with clarity and detail. A Newman projection represents the head-on look down the bond of interest. The circle in the Newman projection represents the atom in front of the bond, and the lines radiating from the center are the bonds of that atom. The bonds of the rear atom emerge from the sides of the circle.

Figure %: How to draw a Newman projection.

Newman projections can be characterized by the angles formed between bonds on the front atom and bonds on the rear atom. Such angles are called dihedral angles. The full 3D shape of any molecule can be described by its bond lengths, bond angles, and dihedral angles. Conformations of Ethane While there are an infinite number of conformations about any sigma bond, in ethane two particular conformers are noteworthy and have special names. In the eclipsed conformation, the C-H bonds on the front and back carbons are aligned with each other with dihedral angles of 0 degrees. In the staggered conformation, the C-H bonds on the rear carbon lie between those on the front carbon with dihedral angles of 60 degrees.

Figure %: The eclipsed and staggered conformations of ethane.

Figure %: Eclipsing interactions in ethane.

Energetically, not all conformations are equally favored. The eclipsed conformation of ethane is less stable than the staggered conformation by 3 kcal/mol. The staggered conformation is the most stable of all possible conformations of ethane, since the angles between C-H bonds on the front and rear carbons are maximized at 60 degrees. In the eclipsed form, the electron densities on the C-H bonds are closer together than they are in the staggered form. When two C-H bonds are brought into a dihedral angle of zero degrees, their electron clouds experience repulsion, which raises the energy of the molecule. The eclipsed conformation of ethane has three such C-H eclipsing interactions, so we can infer that each eclipsed C-H "costs" roughly 1 kcal/mol. Steric Hindrance Eclipsing interactions are an example of a general phenomenon called steric hindrance, which occurs whenever bulky portions of a molecule repel other molecules or other parts of the same molecule. Because such hindrance causes resistance to rotation, it is also called torsional strain. The 3 kcal/mol needed to overcome this resistance is the torsional energy. Note that this figure is very small compared to the energy required to rotate around double bonds, which is 60 kcal/mol (the bond energy of a C-C $\pi$ bond). At room temperature, ethane molecules have enough energy to be in a constant state of rotation. Because of this rapid rotation, it is impossible to isolate any particular conformation in the way that cis- and trans- alkenes can be individually isolated. Although the term "conformational isomer" is sometimes used as a synonym for conformations, conformations of a molecule are not considered true isomers because of their rapid interconversion.

Figure %: Energy diagram for rotation about the C-C bond in ethane.

Figure 1: Newman projection of ethane

A conformational analysis is a study of the energetics of different spatial arrangements of atoms relative to rotations about bonds. Conformational analyses are assisted greatly by a representation of molecules in a manner different to skeletal structures. A representation of a molecule in which the atoms and bonds are viewed along the axix about which rotation occurs is called a Newman projection (Figure 1). In a Newman projection, the molecule is viewed along an axis containing two atoms bonded to each other and the bond between them, about which the molecule can rotate. In a Newman projection, the "substituents" of each atom composing the bond, be they hydrogens or functional groups, can then be viewed both in front of and behind the carbon-carbon bond. Specifically, one can observe the angle between a substituent on the front atom and a substituent on the back atom in the Newman projection, which is called the dihedral angle or torsion angle. In ethane specifically, we can imagine two possible "extreme" conformations. In one case, the dihedral angle is 0 and the hydrogens on the first carbon line up with or eclipse the hydrogens on the second carbon. When the dihedral angle is 0 and the hydrogens line up perfectly, ethane has adopted the eclipsed conformation (Figure 2). The other extreme occurs when the hydrogens on the first carbon are as far away as possible from those on the second carbon; this occurs at a dihedral angle of 60 and is called the staggered conformation (Figure 2).

Figure 2: Conformations of ethane - staggered and eclipsed

Figure 3: Conformations of butane: fully eclipsed, gauche, eclipsed, and anti

The staggered conformation of ethane is a more stable, lower energy conformation than the eclipsed conformation because the eclipsed conformation involves unfavorable interactions between hydrogen atoms. Specifically, the negatively charged electrons in the bonds repel each other most when the bonds line up. Thus, ethane spends most of its time in the more stable staggered conformation.

Conformational analysis of butane

In butane, two of the substituents, one on each carbon atom being viewed, is a methyl group. Methyl groups are much larger than hydrogen atoms. Thus, when eclipsed conformations occur in butane, the interactions are especially unfavorable. There are four possible "extreme" conformations of butane: 1) Fully eclipsed, when the methyl groups eclipse each other; 2) Gauche, when the methyl groups are staggered but next to each other; 3) Eclipsed, when the methyl groups eclipse hydrogen atoms; and 4) Anti, when the methyl groups are staggered and as far away from each other as possible (Figure 3). The fully eclipsed conformation is clearly the highest in energy and least favorable since the largest groups are interacting directly with each other. As the molecule rotates, it adopts the relatively stable gauche conformation. As it continues to rotate, it encounters less favorable eclipsed conformation in which a methyl group eclipses a hydrogen. As rotation continues, the molecule comes to the anti conformation, which is the most stable since the substituents are staggered and the methyl groups are as far away from each other as possible. An energy diagram is a graph which represents the energy of a molecule as a function of some changing parameter. An energy diagram can be made as a function of dihedral angle for butane (Figure 4).

Figure 4: Energy diagram for conformations of butane as a function of dihedral angle

Clearly, the anti and gauche conformations are significantly more stable than the eclipsed and fully eclipsed conformations. Butane spends most of its time in the anti and gauche conformations. There is one final, very important point. At room temperature, approximately 84 kJ/mol of thermal energy is available to molecules. Thus, if the barrier to a rotation is less than 84 kJ/mol, the molecule will rotate. In ethane and butane, the barriers to rotation are significantly less than 84 kJ/mol. Therefore, even though the eclipsed conformations are unfavorable, the molecules are able to adopt them. In reality, since these conformations are not as stable, the molecules will quickly pass through them at room temperature and return a staggered conformation. Molecules are constantly converting between different staggered conformations all the time, quickly passing through eclipsed conformations in between. Thus, in alkanes, no single "true" conformation exists all the time; the molecule instead constantly converts between conformations, spending more time in those that are more stable. This constant conversion lies in stark contract to alkenes, which adopt the cis- or trans- (E- or Z-) conformations and retain them at room temperature; they do not interconvert because the barrier to rotation is too high.