Stereochemistry

B. Tech.
- 2nd Semester
CHEMISTRY-I
Unit-6
Stereochemistry
03-06-2022 1
What is Isomer?
Isomers are the molecules with similar molecular formulae and

Molecular weight.
This is also applicable to Polyatomic ions
Existence of Possibility of Isomers is called Isomerism

Isomers do not necessarily share similar chemical or physical properties. Two main
forms of isomerism are structural or constitutional isomerism, in which bonds
between the atoms differ; and stereoisomerism or spatial isomerism or
Geometrical isomerism or opticalisomerism, in which the bonds are the same but
the relative positions of the atoms differ.
Examples
Geometrical Isomerism/Stereo Isomerism
Coupling constants for Cis and Trans isomers
Optical Activity of Stereoisomers
The ordinary lights are composed of rays of different wavelengths vibrating in all directions perpendicular to the
path of its propagation. These vibrations can be made to occur in a single plane by passing such light through
the polarizing Nicol prism.
Such light whose vibrations occur in only one plane is called plane polarized light
Compounds which rotate the plane of polarized light are called optically active compounds and this
property is known as optical activity. Rotation of plane of polarized light can be of two types.
• Dextrorotatory : If the compound rotates the plane of polarization to the right(clockwise) it is

said to be dextrorotatory (Latin: dexter-right) and is denoted by (+), or ‘d’.
• Laevorotatory : If the compound rotates the plane of polarization to the left(anticlockwise) it is

said to be laevorotatory (Latin: laevus-left) and is denoted by (-) or ‘l’
[α] λt = α/lc or
[α]= specific rotation
t = temperature of measurement
λ=wavelength of the light used
α= observed angle of rotation
l= length of sample tube in decimeter
c=concentration of the sample in g/mL of solution
The term Chiral- The word chiral (Greek word
Chier,meaning hand) is used for those objects which have right
handed and left-handed forms, i.e., molecules which have
“handedness” and the general property of “handedness” is
termed chirality. An object which is not superimposable upon its
mirror image is chiral.
The term Achiral- Object and molecules which are

superimposable on their mirror images is achiral. Achiral
molecule has internal plane of symmetry, a hypothetical plane
which bisects an object or molecule into mirror-reflactive
halves. An object or molecule with an internal plane of
symmetry is achiral.
•
The term Asymmetric center and chiral
center- Three terms are used to designate, a carbon atom
bonded tetrahedrally to four different substituents in a chiral
molecule: Asymmetric atom, chiral center or stereocenter.
III and IV are not enantiomers . they are diasteriomers hence in this case sterio centres
are not chiral centres. Also these are not tetrahedral.
Thus, all chiral centres are sterio centres but all steriocentres are not chiral centres. If a molecule
contains only one chiral centres it must be chiral. Molecule containing two or more chiral centres may
or may not be chiral. For example: meso tartaric acid has two chiral centres but it is achiral.
STEREOISOMERS- Isomers having the same molecular formula but different spatial arrangement of
their atoms are known as stereoisomer. They are of following types:
Enantiomers: Stereoisomers which are non superimposable mirror images of each other are called
enantiomers. Chirality is necessary and sufficient condition for existence of enantiomers. These always exist as
discrete pairs.
Geometrical Isomers:
Geometrical isomers occurs as a result of restricted rotation about a carbon-carbon bond. This is also called cis
trans isomerism.
This isomerism exhibited by variety of compounds such as compound containing double bond C=C, C=N, N=N,
compound containing cyclic structure or compound containing restricted rotation due to steric hindrance.
Conformational isomers: Conformational isomers are the isomers that can be converted into one another by
rotation around a single bond.
Example: eclipsed, gauche and anti butane are all conformational isomers of one another.(eclipsed means that identical
groups are all directly in line with one another, gauche means that identical groups are 60 degree from one another and
anti means that identical groups are 180 degree from one another.)
D, L SYSTEM OF NOMENCLATURE
This nomenclature is mainly used in sugar chemistry or optically active polyhydric carbonyl compounds. This is a
relative nomenclature because all the configurations described with respect to glyceraldehydes. All sugars whose
Fischer projection formula shows the OH group on the right hand side of the chiral atom belong to the D-series.
E-Z isomerism
What is it?
Stereoisomerism occurs when substances have the same molecular formula, but a different
arrangement of their atoms in space. E-Z isomerism is one type of this isomerism. It applies to:
o alkenes and other organic compounds that contain C=C bonds

o cyclic alkanes.
You will be able to identify some of the organic compounds you meet at A Level as cis or
trans isomers. However, this naming system cannot cope with complex situations. For
example, where it is not obvious which groups are on the same side of the C=C bond, or opposite to
each other. This is where the E-Z system comes to the rescue.
What is here?
You can see models of the E-Z isomers of:
•but-2-ene
•1-bromo-2-chloroprop-1-ene
These are chosen to show some of the ideas behind the E-Z naming system. A Level students
should be able to work out whether each isomer is the E isomer or the Z isomer.
E-but-2-ene Z-but-2-ene
R.S. NOMENCLATURE
The order of rearrangement of four groups around a chiral carbon is called the absolute configuration around that
atom. System which indicates absolute configuration was given by three chemists R.S. Cahn, C.K. Ingold and V.
Prelog. This system is known as (R) and (S) system or the Cahn-Ingold Prelog system (CIP). The letter (R)
comes from the Latin rectus (means right) while (S) comes from the Latin sinister (means left). Any Chiral
carbon atoms have either an (R) configuration or a (S) configuration. Therefore one enantiomer is (R) and the
other is (S). A recemic mixture may be designated as (RS), meaning a mixture of the two.
If a double or a triple bond is linked to chiral centre, the involved electrons are duplicated or triplicated
respectively increasing priority
Isomerism in Transition Metal Complexes
The ions or molecules that bind to the central metal ion or atom to form these complexes are called ligands.
The number of ligands bound to the central metal ion or atom is called the coordination number. Transition
metal complexes can have different shapes depending on its coordination number.
The shapes that are common for transition metal complexes formed using monodentate ligands (ligands
which only form one bond to the central metal ion or atom) are tetrahedral, square planar and octahedral , as
shown below. 6-co-ordinated complex ions, in which the central metal is attached to six ligands, have an
octahedral shape.
On the other hand, 4-co-ordinated complex ions, in which the central metal is attached to four ligands, can
either have a tetrahedral or square planar shape. The difference between these 2 shapes lies in the bond
angle— in tetrahedral structures, the bond angle is 109.5 degrees, while in square planar structures, the bond
angle is 90 degrees.
Tetrahedral Square Planar Octahedral
Apart from organic compounds, transition metal complexes also exhibit stereoisomerism, namely
geometric isomerism and optical isomerism. However, geometric isomers are only possible for square
planar and octahedral complexes, but not tetrahedral. Conversely, optical isomers are possible only for
tetrahedral and octahedral complexes, but not square planar. This is summarised in the flowchart

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B. Tech.

Isomers are the molecules with similar molecular formulae and

This is also applicable to Polyatomic ions

Existence of Possibility of Isomers is called Isomerism

• Dextrorotatory : If the compound rotates the plane of polarization to the right(clockwise) it is

• Laevorotatory : If the compound rotates the plane of polarization to the left(anticlockwise) it is

The term Achiral- Object and molecules which are

o alkenes and other organic compounds that contain C=C bonds

Tetrahedral Square Planar Octahedral

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