DYNAMIC STEREOISOMERISM

Atropisomersism: Isomerism caused by freezing /locking the internal rotation about single
Bonds. Free rotation about a single bond was accepted in chemistry since there was no
presence of separate isomers detected in molecules of the kind XYZC-CZYX.
The first isomers detected due to restricted rotation were 2, 2’ dinitro-6,6’ diphenic acid.

The term atropisomers was coined to define the optical isomers of Biphenyls. The term
Atropisomers was coined by Kuhn in 1933
NMR spectroscopy is a very useful technique to detect rotamers.
If the NMR is recorded at lower temperatures the rotamers or Atropisomers give
Different signals.
Two signals corresponding to two isomers appear at lower temperatures where as a
time averaged signal appears at room temperature
Many rotamers can be detected by vibrational spectroscopy. Hence all compounds may
Exhibit atropisomerism
Different isomers of symmetrical tetrabromoethane were crystallised at lower
Temperatures.
The equatorial chlorocyclohexane and axial chlorocyclohexane were differentiated
By the isolation of the former at -150oC
Whereas there is equilibration of the two at room temperatures.
Atropisomers which exist at room temperatures have the free energies of activation
Of more than 23Kcalmol -1.
Atropisomers are detectable by NMR if the half lifes exceed by 10 -2 sec.

Ex: Gossypol the main pigment of cotton seeds

Biphenyls are not planar. These are the class of compounds that display conformational
Enantiomorphism. One benzene ring being slightly twisted or canted in relation to the
other as a consequence of steric crowding.

In order to convert each conformer to the other it would have to pass through the
High energy sterically hindered coplanar conformation.
If the groups present at these positions are bigger the barrier to rotation is more
And they will not interconvert easily. If the energy barrier is 16-19 Kcal/mol two isomers
can interconvert spontaneously at room temperature.
Atropisomerism is not a phenomenon restricted to biphenyls, many other
systems like binaphthyls exhibit atropisomerism.

A classic example of an atropisomeric binaphthyl is the ligand BINAP, the

development of which earned Noyori a share of the Nobel Prize for Chemistry in
2001. Once the atropisomers have been separated, BINAP can be used as a
chiral catalyst for the asymmetric hydrogenation of C=C and C=O bonds
Biphenyls are chiral even though there is no chiral center.
Their chirality is due to restricted rotation about the central bond.
With large groups at the ortho positions they cannot rotate freely and give rise
to atropisomerism and chirality.
In these compounds the two rings are perpendicular to each other.

H3C NH2 Ac2O HO2C NHAc O

C NH
H2N CH3 Oxidation AcHN CO2H HN C
O

Optically active Optically active Optically inactive

The optical activity is lost in the above biphenyl as the two rings are joined
By the ortho poistions which make them to stay in a planar conformation
Suitably substituted allenes are another class of compounds which show
chirality in the absence of a chiral center.

What is the point group of allene and 1,3 dichloroallene?

An amine with three different substituents and a lone pair cannot be superimposed
on its mirror image, but they have not been resolved. Explain why?

The amine rapidly interconverts through a sp2 hybridized Nitrogen

N
Atom and the non bonding electrons occupy the p orbital.

The process is termed the pyramidal inversion at trivalent Nitrogen. N

Do you find the same phenomenon in the given example? CH2CH3

H CH3
C

NH2
CH2CH3
H CH3
What about the molecule N

Ph
Invertomers are conformers which interconvert by inversion at an atom with
lone pair of electrons.
 H3C CH3
N Br Br N

In small rings like aziridines the Nitrogen cannot invert because of steric constraints.
Hence they can be resolved into enantiomers.
The activation energy required for inversion is much higher in phosphines and cannot
Interconvert at ordinary temperatures. Hence many optically active phosphines have
been prepared. At higher temperatures they may racemize.
Dipole moment is due to an unbalanced charge distribution in its molecules.
In principle any two distinct atoms in a molecule will give rise to local dipole.
As any two different atoms differ in electronegativity.

But it will have a dipole moment only if the local dipole of any X-Y grouping in one region
is not compensated by an opposite local dipole elsewhere in the molecule.

Symmetry properties dictate whether this will or will not be the case.

Molecules with centre of symmetry ---- will not have dipole moment
Hence Sn with n=even(including Si=C2) cannot have a permanent dipole moment.

Cn: Molecules with an axis of symmetry can have a dipole moment but

there should not be a plane perpendicular to this( σh)

There should not be a axis perpendicular to this axis

Hence Cnh, Dn, Dnh and Dnd all these symmetry groups do not have a permanent
Dipole moment.
Only molecules with Cn(includingC1), Cs and Cnv point groups can have a permanent
Dipole moment.

Ex: trans 1,4 dibromocyclohexane (C2h point group) does not have a dipole moment.

Trans 1,2 dibromocyclohexane (c2 point group ) has a dipole moment.

Br
Br
Br
Br Br
Br

Br Br
Molecular symmetry should not be averaged for deciding whether a molecule has
dipole moment or not.

Where as while deciding upon the chirality of a molecule it should be considered.

By mistake it should not be thought that equally populated gauche forms of a
molecule cancel each other.
Rotation of Polarized light:
Cn(C1), Dn and less common groups like T, O, I can give rise to optical rotation.
What is the point group of toluene?

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