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Configuration and Conformation
• Changing the configuration of a molecule always means that bonds are broken • A different configuration is a different molecule • Changing conformation of a molecule means rotating about bonds, but not breaking them • Conformation of a molecule are rapidly interconvertible, and are all same molecule.
Do the bond angles and bond lengths in ethane limit us to a single arrangement of atoms? Answer is NO. If the various arrangements do not differ much in energy, then the molecule is not restricted to any one of them, but can change freely from one to another by rotation about the C-C bond, we call it a free rotation about the C-C single bond.
1 .5 4Α
.Different arrangements of atoms that can be converted into one another by rotation about single bonds are called conformations Certain physical properties show that rotation is not quite free: there is an energy barrier of about 12 kJmol-1 for rotation around C-C bond in ethane.
. the energy barrier must be over 100 kJ/mol.Barriers to Rotation Around Different Type of Bonds H H H H H H N CH3 H O CH3 12 KJ/mol 30 KJ/mol 85 KJ/mol 260 KJ/mol For conformations to interconvert slowly enough for them to exist as different compounds.
why? .An analysis of the energy change that a molecule undergoes as groups rotate about single bonds is called conformational analysis The rotational barrier along C-C bond in ethane is 12 kJ/mol where as its 45 kJ/mol in case of CCl3-CCl3.
Representation of Conformations Conformations are represented by two kinds of 3-dimensional formulas 1. Sawhorse formula: In this representation the bond between two atoms (Carbon-Carbon) form an oblique angle and indicate spatial orientation by showing all the other bonds (C-H) H H H H H H H H H H H H Eclipsed Staggered .
• The carbon farther away is represented by a circle. which we will call projected bond. Newman Projection formula: It’s a type of planar projection along one bond.2. • Carbon atom nearer to the viewer is at the junction of front three bonds. bonds attached to this carbon join the edge of circle and do not meet in the centre . If we view ethane molecule in Newman Projection along the C-C bond then this C-C bond is projected bond.
H H H H View along this C-C bond H H H H H H H H H H H H H H .
Notice that when we draw the eclipsed conformation we have to offset the front and back bonds slightly to see the substituents clearly. In reality. In eclipsed conformation θ is 0º and in staggered conformation θ is 60º. .HH H H θ H Eclipsed H H 1 Staggered H H H H 2 H Dihedral angle (θ): Angle between C-H bond θ at the nearer carbon and a C-H bond at the farther carbon. one is right behind other.
and reaches a maximum at the eclipsed conformation. increases with rotation. Potential Energy H H H H H H HH H H H H H H H H H H .The potential energy of the molecule is at a minimum for the staggered conformation.
The higher energy associated with eclipsing of the bonds is called torsional energy or torsional strain. The barrier to rotation is called the torsional barrier of the single bond. The 12 kJmol-1 torsional barrier between the two conformations is not very high.Any molecule spends most of its time in the most stable conformation. .
. Instability of eclipsed conformation is thought to be due to repulsive interaction between bonding pairs of electrons (C-H bonds).Even at room temperature the fraction of collisions with sufficient energy is large enough so that a rapid interconversion between staggered arrangements is possible. Relative instability of the eclipsed conformation is said to be due to torsional strain.
and any rotation away from the staggered conformation is accompanied by torsional strain. hydrogen bonding etc.As the H’s of ethane are replaced by other atoms or group of atoms. dipoledipole interaction. other factors affecting the stability of conformations appear : van der Waals attraction or repulsion. . But the tendency for the bond orbitals on adjacent carbons to be staggered remains.
. we see a molecule similar to ethane.Conformational analysis of n-butane If we focus our attention on C2-C3 bond of n-butane. but with a methyl group replacing one hydrogen on each carbon.
A factor besides torsional strain comes into play to affect conformational stabilities.As with ethane. But. in n-butane staggered conformations have lower torsional energies and hence are more stable than eclipsed conformations. due to the presence of the methyl groups. 2. two new points are encountered: 1. There are several different staggered conformations. .
conformation conformation conformation conformation conformation Conformation Conformations of n-butane .
though are different. (a). in which the methyl groups are only 600 apart. in which the methyl groups are as far apart as they can be (dihedral angle 1800). and are of the same stability. There are two gauche conformations.There is the anti conformation. Conformations (c) and (e) are mirror images of each other.(c) and (e). .
Conformational Analysis of n-Butane .
..e.The anti conformation is more stable than the gauche by 3. under these conditions. But in a gauche. van der Waals forces are repulsive and raise the energy of the conformation. are thrown together closer than the some of their van der Waals radii. the methyl groups are crowded together i.8 kJmol-1. Both are free of torsional strain.
.We say that there is van der Waals repulsion (or steric repulsion) between the methyl groups. and that the molecule is less stable because of van der Waals strain (or steric strain). Van der Waals strain can not only affect the relative stabilities of various staggered conformations. but also the heights of the barriers between them.
they too are stereoisomers. a pair of conformers can either be mirror images of each other or not. . Since conformers differ from each other only in the way their atoms are oriented in space.Conformational isomers Different conformations corresponding to energy minima are called conformers. Like stereoisomers of any kind.
Conformational Stereoisomerism CH3 H H H CH3 a om e er t as i CH3 H3C H s er H a di s te re om s er d CH3 enantiomers H H H CH3 c H H H H e .
The gauche conformers. are mirror images of each other and hence are conformational enantiomers. one anti and two gauche.n-Butane exists as three conformers. Conformers (a) and (c) or (a) and (e) are not mirror images of each other. . (c) and (e). and hence are conformational diastereomers.
• Most molecules. the greater is the fraction of the molecules that will be in that conformation. in a zig-zag fashion. The tendency to assume a staggered conformation causes carbon chains to orient themselves.• Conformers can not be separated • The relative number of molecules in a particular conformation at any one time depends on the stability of the conformer. therefore are in staggered conformations. . the more stable the conformer.
between 1 & 2 and 2 & 3? . H H H H CH2CH3 H H H H H H CH2CH3 H H3CH2C H H H H 1 2 3 Do they have same energy? What about eclipsed conformers? What is relation between 1 & 3.Draw the three staggered conformer of n-butane for rotation around C1-C2 bond.
Conformations of Cycloalkanes A carbon when bonded to four other atoms. Cyclopropane Cyclobutane Cyclopentane . the angle between any pair of bonds is the tetrahedral angle 109.50.
but must be compressed to 600 or 900 to fit the geometry of the ring. and hence to be unstable compared with molecules in which the bond angles are tetrahedral. .In cyclopropane or cyclobutane. These deviations of bond angles from the “normal” tetrahedral value cause the molecule to be strained. one pair of bonds to each carbon cannot assume the tetrahedral angle.
600 = 49.Cyclopropane and cyclobutane undergo ring opening reactions since these relieve the strain and yield the more stable open chain compounds. Because the deviation of the bond angles in cyclopropane (109. more unstable. and more prone to undergo ring opening reactions than is cyclobutane.50 .50).50) is greater than in cyclobutane (19. . cyclopropane is more highly strained.
are somewhat larger than the tetrahedral angle.50 . The angles of a regular hexagon (1200) considered to be planar.The angles of regular pentagon (1080) are very close to the tetrahedral angle cyclopentane therefore. as such. should be virtually free of angle strain. . cyclohexane molecule should have in it an angle strain of 10.
.50. so that each bond angle of carbon can be 109. so as to relieve itself of the angle strain.The cyclohexane ring is not planar but is puckered.
First is the chair form. . Looking at each of the carbon-carbon bonds.Let us make a model of the molecule and examine the conformations that are free of angle strain. we find in every case the bonds are perfectly staggered.
is therefore. of nearly every derivative of cyclohexane.This conformation is thus not only free of angle strain but free of torsional strain as well It has minimum energy. a conformational isomer. The chair form is most stable conformation of cyclohexane. . and indeed.
we see sets of exactly eclipsed bonds. it can be converted into boat conformation. Sighting along either of the two carboncarbon bonds.On flipping the chair conformation. and hence we expect considerable torsional strain equal to two ethane molecules .
. there is van der Waals strain due to crowding between the “flagpole” hydrogens. which lie considerably closer than the sum of their van der Waals radii. The boat conformation is thus less stable than the chair conformation.In addition.