CONFORMATIONAL ISOMERISM. Carbon-carbon single bond in alkanes is a sigma bond formed by the overlapping of sp’ hybrid atomic orbitals along the inter-nuclear axis. The electron distribution in such a bond is symmetrical around internuclear axis; so that free rotation of one carbon against the other is possible without breaking sigma or single covalent bond. Consequently such compound can have different arrangements of atoms in space, which can be converted into one another siniply by rotation around single bond, without breaking it. These different arrangements are known as Conformational Isomers ar Rotational Isomers or Conformers. Since the potential energy barrier for their inter-coversion is very low, il is not possible to isolate them at room temperature. At least 60-85 kI/mole must be the energy difference between two conformers to make them isolatable at room temperature. Hence, conformations can be defined as different arrangements of the atoms which can be converted into one another by rotation around single bonds Newman and Sawhorse representations for the conformations of ethane Alkanes can have an infinite number of conformations by rotation around carbon-carbon single bonds. In ethane two carbon atoms are linked by a single bond and each carbon atom is further linked with three hydrogen atoms. If one of the carbon atoms is allowed to rotate about carbon- carbon single bond keeping the other carbon stationary, an infinite number of arrangements of the hydrogens of one carbon, with respect to those of the other, are obtained. All these arrangements are called conformations (Bond angles and bond lengths remain the same). Newman reppresentation ‘This can be easily understood with the help of Newman Projection formulae. The molecule is viewed from front to back in the direction of carbon-carbon single bond. The carbon nearer to the eye is represented by a point and three hydrogen attached to it are shown by three lines at an angle of 120° to one another. The carbon atom away from the eye is represented by a circle and three hydrogens attached to it are shown by shorter lines at an angle of 120° to each other, Out of infinite number of conformations, Newman Projection formulae for two extreme cases are as shown below: H H H # H H H H iH " Staggered Eclipsed Newman Projection Formulae for conformations of ethane. The conformation in which the H atoms of two carbons are as far apart as possible, is known as Staggered conformation and the conformation in which the H atoms of back carbon are just behind those of the front carbon is known a Eclipsed conformation. These are converted into one another by rotation of one carbon against the other through 60°. The other conformations, in between these two, are known as skew conformations.Sawhorse representation {n this representation, the molecule is visualised slightly from above and from the right and then projected on the paper. The bond between two carbons is drawn diagonally and is a bit longer for the sake of clarity. The lower left hand carbon is taken as front carbon and the upper right hand carbon is taken as back carbon, The Sawhorse representation of staggered and eclipsed conformations of ethane are given below i H Ht H Staggered Belipsed Sawhorse representation for conformations of chtene Pitzer in 1936 found that the rotation is not completely free. Rather there exists a potential energy barrier which restricts the free rotations. It means that the molecule spends most of its time in the most stable staggered conformation and it spends least time in the least stable eclipsed conformation; the energy difference being 12 kL/mole in the case of ethane. Edlipsed Staggered Staggered ———~ Potential energy Rotation ~———> Rotational or torsional energy of ethane The energy required to rotate the molecule about carbon-carbon bond is called rotational or torsional energy. ference between conformation and configuration Conformation Structures containing different arrangement of atoms of « molecule in space which can arise by rotation about a single bond are called conformers. For example ethane exists. in different conformations called staggered, eclipsed and skew conformations. The energy difference between different conformers is rather small. This phenomenon is called conformation. The property of conformation is also exhibited by n-butane, cyclohexane, stilbene dichloride etc. DilConfiguration Structures of a compound differencing in the arrangement of atoms or groups around a particular atom in space are called configurations. Enantiomers, distereomers and geometrical isomers come under this category. For example d-and /-lactic acids are configurations of lactic acid (e t HO. ¢ —H H i —OH COOH coon #lactic acid hlactic acid cus and trans butenes are configuration of butene cH, cH, H. CH, Dee ened’ H H cHy H cis-2-butene trans-2-butene Factors affecting relative stability of conformations The following factors play a vital role in the stability of conformations 1. Angle strain. Every atom has the tendency to have the bond angles that match those of its bonding orbitals. If there is any deviation from this normal bond angle, the molecule suffers from angle strain, Conformations suffering from angle strain are found to be les stable. 2. Torsional strain, There is a tendency on the part of two carbons linked to each other to have their bonds staggered. That is why the staggered form of any molecule like ethane, n-butane + most stable. As the bonds of two, connected carbons move towards eclipsed state, a rorsional sirain is set up in the molecule thus raising its energy. Thus the staggered conformations have the east and eclipsed the highest torsional strain. The energy requited to rotate the molecule around che carbon-carbon bond is called forsional energy: 3. Steric strain (van der Waals' Strain). Groups attached to two linked carbons can interact 1 different ways depending upon their size and polarity, These interactions can be attractive or cepulsive. If the distance between the groups or atoms is just equal to the sum of their van der Waals’ radii, there will be attractive interactions between them. And if these atom or groups arc srought closer than this distance, there will be repulsions leading to van der Waals’ strain or steric svain in the molecule. 4. Dipole-dipole Interactions. Atoms or groups attached to bonded carbons orient or position :hemselves to have favourable dipole-dipole interactions. It will be their tendency to have maximum dipole-dipole attractions. Hydrogen bond is a particular case of powerful dipole-dipole attractions. The stability of a conformer is determined by the net effect of all the above factors. Conformations and change in dipole-moment of 1, 2- temperature ‘The conformations of 1, 2 dibromoethane have been extensively studied by dipole-moment measurement. The conformations are depicted as under : ibromoethane withIm the liquid state, the percentage of anti forms is 65 corresponding to conformational free energy of 3.5 kJ mol! in favour of anti. Br Br Br H H Hn Br Br, H Ww br OH a Hoy H anti gauche gauche stability of anti-form is due to combined effects of steric factor and dipole-dipole interactions. It goes in favour of formation of anti- conformer. Dipole movement increases with increase of temperature, Conformations of butane n-butane is an alkane with four carbon atoms, which can be considered to be derived from ethane by replacing one hydrogen on each carbon with a methyl group. If we consider the rotation about the central carbon-carbon bond (C, — C, ), the situation is somewhat similar to ethane; but n-butane has more than one staggered and eclipsed conformations (unlike ethane which has only one staggered and one eclipsed conformation). Newman Projection formulae for various staggered and eclipsed conformations of n-butane are as given below CH, H H. JH H. H CH, oH H H Hoy, H ot Hoy, Cth . Compleely Partially Partially staggered or staggered or ant form eelipaed em gauche form or skew form s 1 " nt 4H H CH, i H H H x H ‘H H. H cu, 7 CH,CH, CH, H CH Completely ly staggered Panially eclipsed form or gauche eclipsed orm v v vl ‘The completely staggered conformation, (1) also known as anti form, is having the methyl goups as far apart at possible, Let us see how these forms have been obtained. Let us start from structure I Holding the back carbon (represented by circle) fixed along with its groups, —H,—-H and —CH,, rotate the front carbon (shown by a dot) in clockwise direction by an angle of 60°. Groups attached to it will also move. Partially eclipsed form (1) is obtained. In this conformation (11), methyl group of ‘one carbon is.at the back of hydrogen of the other carbon. Further rotation of 60° leads of a partially staggered conformation (I1!), also known as gauche form, in which the two methyl groups are at an angle of 60°. Rotation by another 60° gives rise to a fully eclipsed form (IV) having two methyl groups at the back of each other, Further rotation of 60°, again leads to partially staggered or gauche form (V) having methyl groups at an angle of 60° (as in IMf), Still further rotation of 60° leads topartially eclipsed form (V1), having methyl group of one carbon at the back of hydrogen of the other (as in 11). If'a further rotation of 60° is operated (completing the rotation of 360°), again form I is obtained. Of course, there will be an infinite number of other conformations in between these six ‘conformations (1 to VI). (Gauche form is also known as skew form). ‘Out of these six conformations, the completely staggered or anti conformation (1) is most stable and partially staggered ot gauche conformation (III or V) is slightly less stable: the energy difference being only 3.8 kJ/mole. On the other hand the completely eclipsed conformation (IV) is least sthble and partially ectipsed conformation (il or VI) is slightly more stable, agein the energy difference being 3.8 ki/mole. (This is due to presence of steric strain between two methyl groups). The energy difference between most stable conformation (I) and least stable conformation (IV) is about 18.4 ki/mole while that between I and IL,(or VI) is about 14.6 ki/mole Completely eclipsed WV Partially Partially eclipsed il eclipsed VI Potential energy oa ROTO DAF Rotation ————> Rotational ot torsional energy of n-butane ‘Thus at ordinary temperature, n-butane molecule exists predominently in anti form with some guache forms. Conformational enantiomers of 2, 3-Dimethylbutane and 2, 2, 3-Trimethylbutane Conformational isomers of 2,3-Dimethylbutane Me Me Mc " i: 7 P * , Me yep H Me 4 H Me ye H 1 1 1 Structure I is supposed to have maximum stability out of these three isomers, II and III are conformational enantiomers (mirror-images) also. This can be visualized after rotation of III as a whole. ‘Conformational isomers of 2, 2, 3-Trimethylbutane