D. D.

Grove

Visualizing Molecules

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Conformations, Saw Horse, and Newman Projections Chemists have devised a few different ways to visualize molecules. Consider ethane. Lets look at its structure beginning with the condensed formula: CH3CH3 Now, this formula actually does indicate the fact that the carbon atoms are bonded to each other, so we can now draw a Lewis structure, making sure the octet rule is obeyed. The structure below indicates clearly the
H H C H H C H H

different carbons align with one another; we say they are eclipsed. In the second structure the hydrogen atoms staggered in an equal manner. Again, study the examples until you see what I am talking about.

rotate about C-C bond

tilt and look end-on

tilt and look end-on

atom-to-atom connectivity and thus represents only 2-dimensional structure. The Lewis structure tells us nothing about the 3-dimensional shape of the compound. If we remember that carbon in alkanes is tetrahedral, we can construct a model of the ethane, a 3-dimensional model. Our first attempt at this gives a model like the one below. The blue portion of the model represents carbon atoms and the white represent hydrogen atoms. Where blue meets white indicates a bond between carbon and hydrogen. The middle long blue bond is the C-C bond of ethane. Now, remember,

eclipsed

These structures have different arrangements of the hydrogen atoms

staggered

The two structures above are referred to as conformations. Conformations are different spatial arrangements of atoms in a molecule of given constitution brought about by rotation around single bonds. In the case above, the two conformations result from rotation around the CC bond. The models above are so useful in examining structures of organic molecules that we give them special names and we frequently draw similar representations on paper in our discussions of chemistry. The first representations above are called saw-horse projections because they look like the saw horses one might use in carpentry. We draw in the same way they are shown above. The letters A-F have been added as substituents.

There is free rotation about the C-C bond, so the positions of the hydrogens on one carbon relative to those on the other carbon can changeand does. Look carefully at the pictures above and see the difference in the relative positions of the hydrogen atoms. Looking end-on, one can easily see the differences. The two structures above are not the same. In the first case the hydrogen atoms on the Chapter 13 H:\MyFiles\wpdocs\organic1\Lec Notes\visiualizing molecules.doc

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Visualizing Molecules
H D D H C F E A B C F B E H H H H H H H H H H

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eclipsed

eclipsed

staggered

staggered
Study these two sawhorse projections until you understand how these are related to the original models and the Lewis and condensed structures with which we started. Shown below are the Newman projections derived from the sawhorse projections. Again, you want to be able to go from sawhorse to Newman in your drawings and the reverse. We will return to the Newman projections shortly.
HH H H H eclipsed H H H H staggered H H

Understand that the saw horse projections are 3-dimensional; they are perspective drawings. If we tilt the eclipsed conformation so the closest carbon to us is right in front of our eye and sight down the C-C bond we get what is called a Newman projection as shown below. The circle represents the front carbon. The bonds that meet in the center of the circle are on the front carbon; the center of the circle locates the position of the front carbon. The back carbon is not visible because it is covered by the front carbon; thus, the bonds from the back carbon emanate from the edge of the circle. The bonds in the back are offset just slightly so we can see them, but understand that atom-pairs A/F, B/E, and C/D are actually eclipsed.
DC A A F eclipsed B E F C staggered D B

Dihedral Angles One way to define and describe the structure of objects is by considering angular disposition of various components. In the case of molecules we often use dihedral angles. A dihedral angle is the angle between two defined planes. Now, recall that planes are composed of three points; in the case of molecules the points will be atoms. The structures below define two planes (#1 and #2). The red lines outline the two planes. Study the figures until you see the planes and note that they are different.

You want to study both saw horse and Newman projections until you are comfortable with them and can draw both with some facility. It is very important that you understand these two projection types, what they show, what they dont, etc. Lets apply the sawhorse and Newman projections to our molecule of ethane. Again, where the three bonds meet, a vertex, is a carbon atom; its really there we just dont write a C. Chapter 13 H:\MyFiles\wpdocs\organic1\Lec Notes\visiualizing molecules.doc

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D. D. Grove
H 3 1 H H H H H H H H 1

Visualizing Molecules

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determined using sawhorse projections. It doesnt matter what the atoms at the end of the C-X bonds are (in this case all Hs) and often we are concerned with only two groups on adjacent atoms.
H3

2 plane #1

2 plane #2

Consider 1,2-dichloroethane and draw the Lewis structure. Are there different conformations of this compound? Start by drawing and
H H C H Cl

ClCH2CH2Cl Lets place the planes on the same structure and see if we can determine the dihedral angle they make. Well, its difficult to determine the dihedral angle from the drawing shown. We know from above that the two drawings below will define the same dihedral angle, so we need to determine angle 313. We can discern from the Newman projection
H 1 H H3 H H H 3' dihedral angle H3

Cl C H

3H

examining a sawhorse projection for the molecule. Start with a staggered framework that includes the two carbon atoms. Locate the bonds that stick straight up and straight down then add the chlorine atoms at the end of these bonds. Now place the hydrogen atoms at the end of the other bonds to obtain the sawhorse projection shown. Convert the sawhorse projection to a Newman projection and determine the dihedral angle between the chlorine atoms.
Cl Cl H H H H H H Cl Cl H H

that this angle is a third of a circle, so it must be 120E. The dihedral angle between plane #1 and plane #2 in the second example above is 120E. Work at this angle stuff until you understand it completely. Another way to determine dihedral angles is to examine the Newman projections. Consider the fact that the circle representing the front carbon is divided into six segments, and that a circle has 360E in it: 360/6 = 60E. So, each segment, defined as shown, is 60E. Two segments would be 120E, three segments would be 180E, etc. Relate this to what we
H H 5 H 4 H staggered 3 6 1 2 H H

staggered

anti

It should be clear from inspection that the dihedral angle between the chlorine atoms is 180E; they point toward opposite ends of a line that contain the atoms. Substituents that are 180E are referred to as being anti (think of as meaning opposite). The conformation shown above for 1,2-dichloroethane is the anti conformation. The anti conformation is one of the several possible staggered conformations. Lets generate another conformation by rotation about the C-C bond. Take the sawhorse projection for the anti conformation of 1,2dichloroethane and, holding the front carbon where it is, rotate the back carbon (w/ substituents) clockwise by 120E. You should have a new staggered conformation, the one shown below. A Newman projection

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Conformational Analysis

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Visualizing Molecules
Cl H Cl H H Cl Cl H H H fully eclipsed fully eclipsed H H H

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shows that the chlorine atoms are 60E apart (1 piece of the pie!). This conformation is clearly different from the anti conformation and goes by the name gauche.
H H H H H H Cl H Cl Cl Cl

staggered

gauche

the two chlorine atoms are themselves eclipsed, we call this conformation fully eclipsed. As before, we hold the front carbon and substituents still and rotate the back carbon by 120E and obtain the conformation below.
H HCl Cl H Cl H H H eclipsed H eclipsed H

Note that both anti and gauche are staggered conformations, but they are different staggered conformations. These conformation represent different structures of 1,2-dichloroethane obtained by rotation about a C-C single bond. Lets rotate the back carbon of the sawhorse projection another 120E. When we do this we get a second gauche conformation. The dihedral angle the chlorine atoms make is again 60E. So weve now generated three staggered conformations, one anti and two gauche. What about the eclipsed conformations?
H H Cl H H H H Cl Cl Cl H H

Cl

In this eclipsed conformation there are two H/Cl eclipsing interactions and there is no Cl/Cl eclipsing interaction. Rotation of the back carbon again by 120E gives a third eclipsed conformation where we have two H/Cl eclipsing interactions. So we have
H HCl Cl Cl H H Cl H eclipsed H eclipsed H

staggered

gauche

The eclipsed conformations are generated in the same way the staggered conformations were generated and, not surprisingly, we find that there are three distinct staggered conformations. Lets consider the eclipsed conformation where the chlorines are both pointing upward. Because Chapter 13 H:\MyFiles\wpdocs\organic1\Lec Notes\visiualizing molecules.doc

three distinct eclipsed conformations, one fully eclipsed and two partially eclipsed. Again, note the structural differences between the fully eclipsed and the partially eclipsed. The chlorine atoms point in different directions, Conformational Analysis

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Visualizing Molecules
H H Cl Cl H
H Cl Cl H H

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relative each other. This feature of chemical structure is very important. For instance, enzymes and proteins only function properly when they are in a certain conformationalter the conformation of an enzyme and you may destroy its function. So, what determines the preferred conformation under a specified set of conditions? Energy! Conformational Analysis and Potential Energy We have to consider the relative potential energies of the different conformations. To do this it is best to use what are called space-filling molecular models. These models take into account the fact that the electron clouds of atoms take up space; they have a volume. These models show that atoms are not points in space. The three

gauche

seeing here. Again, you can see that the green chlorine atoms are quite a bit larger than the carbon atoms and rather large compared to the little hydrogen atoms. You can also see that it looks that there is some interaction between the defined volumes of the chlorine atoms. They appear to be bumping into each other. If we rotate the molecule to examine it on its side we can clearly see the Cl/Cl-bump. What would you

structures above are different views of the anti conformation of 1,2dichloroethane. The chlorine atoms are green, hydrogens white, and the carbons are cyan. One can clearly see that the chlorine atoms are bigger in volume than either the hydrogen or carbon atoms. One can also see that the chlorine atoms point in opposite directions (clear in the first rendering). The second rendering is the first rotated counterclockwise 90Eabout a vertical axis. One can again clearly see that the chlorine atoms point in opposite directions, 180Eapart. The last rendering is the second rotated toward you 90E about a horizontal axis. Look at these models until you understand what it is you are looking at. Relate these space filling models to the sawhorse and Newman projections for the anti conformation of 1,2-dichloroethane. The space-filling model and Newman projection are shown for one of the gauche conformations of 1,2-dichloroethane. Understand what you are

expect the relative potential energies of the two conformations to be? Do the anti and gauche conformations have the same energy content? They have the same atoms and the same atom-to-atom connectivity, so why wouldnt they have the same energy? Since the volume that defines the size of the chlorine atom is actually electron density, the conformation where these electron clouds impinge upon one another would be expected to be of higher potential energy. We expect there to be electrostatic repulsion between the two chlorine atoms. We therefore anticipate that the gauche conformation will have a higher potential energy than the anti. The potential energy diagram below illustrates this and indicates that there is a 1.3 kcal/mol difference in energy between the two conformations.

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Visualizing Molecules
eclipsed: 1-H/H, 2-H/Cl transition state gauche gauche 1.3 kcal/mol anti

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PE

PE
anti

1.3 kcal/mol

The process that converts the anti conformer to the gauche conformer is rotation about the C-C bond. If one follows this process closely it is seen that the molecule must pass through an eclipsed conformation midway through the rotation process. The eclipsed conformation is a
Cl H H Cl H H H Cl H H H Cl H Cl H H

Now lets go from one gauche conformation to the second gauche conformation. This is shown below. Again, think of this as just a mechanical rotation of models. In this case we encounter a fully eclipsed conformation as a transition state. The specific eclipsing interactions are 1-Cl/Cl and 2-H/H. One would expect a Cl/Cl eclipsing interaction to be
H H H H H H H H H Cl Cl Cl Cl H H

Cl Cl

Cl

anti min.

eclipsed max.

gauche min.

gauche min.

fully eclipsed max.

gauche min.

transition state in the process; it represents a maximum on the potential energy curve (see below). Think about this rotation as just a mechanical phenomenon: to go from anti to gauche, the molecule MUST pass through an eclipsed conformation. The specific eclipsing interactions are 1-H/H and 2-H/Cl.

particularly bad (overlapping electron clouds) rendering this conformation even higher in energy than the partially eclipsed conformation.
fully eclipsed: 1-Cl/Cl, 2-H/H transition state

gauche

gauche 1.3 kcal/mol

PE
anti

dihedral angle

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Conformational Analysis