BITS Pilani

Pilani Campus

CHEM F111 General Chemistry

Lecture 24
Dr. Ajay K. Sah
BITSPilani, Pilani Campus

CONFORMATIONS

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Conformations
Two methyl groups are not fixed in a
single position.
They rotate about the sigma bond
connecting two carbon atoms, maintaining
the linear bonding overlap.

The different arrangements formed by

rotation about single bond are called
confomations.
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Conformations

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Conformations
Conformations are represented by
two kinds formulas
(1) Sawhorse formula
(2) Newman Projection formula
H

model

Newman
projection

sawhorse
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Newman Projection

Viewed from end

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Conformations
Dihedral angle (): Angle between the C-H
bond on the front carbon atom and C-H
bond on the back carbon atom in Newman
projection.
Eclipsed conformation: (= 00)
Staggered conformation: (= 600)
Skew conformation: (= anything else)

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Newman Projections

Eclipsed

Staggered

Skew
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Sawhorse Structures

Eclipsed

Staggered

Skew
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Conformations
Conformational
analysis:
study
energetics of different conformations.

of

Potential Energy of the molecule:

Minimum for the staggered conformation

Increases with rotation

Maximum at the eclipsed conformation
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Conformational Analysis of ethane

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Conformations
Torsional Strain:

It is the resistance to twisting (torsion)

as ethane rotates toward an eclipsed
conformation, the energy corresponding to
this is called torsional energy.
For ethane molecule torsional energy
is about 12.6 kJmol-1.
The lowest-energy conformation is
most prevalent.
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Conformations
As the Hs of ethane are replaced by
other atoms or group of atoms, other
factors
affecting the
stability
of
conformations appear: van der Waals
attraction or repulsion, dipole-dipole
interaction, hydrogen bonding etc.

But tendency for the bond orbitals

on adjacent carbons to be staggered
remains, and any rotation away from the
staggered conformation is accompanied
by torsional strain.
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Coformations of propane

Increase in torsional strain (13.8kJ/mol)

due to the more bulky methyl group.
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Conformational Analysis of propane

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Conformations of n-Butane
Free rotation around C2-C3 bond

n-Butane Conformation
Highest energy has methyl groups eclipsed.
Steric hindrance
Dihedral angle = 0 degrees

Totally eclipsed

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n-Butane Conformation
Gauche, staggered conformation
Methyls closer than in anti conformation
Dihedral angle = 60 degrees

gauche
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n-Butane Conformation
Methyl groups eclipsed with hydrogens
Higher energy than staggered conformer
Dihedral angle = 120 degrees

eclipsed
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n-Butane Conformation
Lowest energy has methyl groups anti.
Dihedral angle = 180 degrees

anti

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n-Butane Conformation

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Conformational analysis of n-butane

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Conformational analysis of n-butane

Totally eclipsed conformation is
about 6 kJ higher in energy than other
eclipsed confomations because of steric
strain or steric hindrance.

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Higher Alkanes
Anti conformation is lowest in energy.
Straight chain actually is zigzag.
H H H H H
C
C
C
C
C
H
H
H H H H
H

CH3CH2CH2CH2CH3

Since conformations differ from each other

only in the way their atoms are oriented in
space, they too are stereoisomers.
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Conformations of Cycloalkanes

In cyclopropane or cyclobutane, one

pair of bonds to each carbon cannot
assume the tetrahedral angle, but must be
compressed to 600 or 900 to fit the
geometry of the ring.
These deviations of bond angles
from the normal tetrahedral value cause
the molecule to be strained, and hence to
be unstable compared with molecules in
which the bond angles are tetrahedral.
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Conformations of Cycloalkanes

Cyclopropane

Cyclobutane

Cyclopentane
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Conformations Of Cycloalkanes

Angle strain

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Conformations Of Cycloalkanes

Torsional strain because of eclipsed hydrogens

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Conformations Of Cycloalkanes

Torsional strain partially relieved by ring-puckering

Ring Strain = Angle strain + Torsional strain

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Conformations Of Cycloalkanes

Deviation of the bond angles

Cyclopropane (109.50 - 600 = 49.50)

Cyclobutane (109.50 - 900 = 19.50)
Cyclopropane and cyclobutane undergo
ring opening reactions since these relieve
the strain and yield the more stable open
chain compounds.
Cyclopropane is more highly strained,
more unstable, and more prone to undergo
ring opening reactions.
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Conformations Of Cyclohexane

The ring is not planar but is puckered, so

as to relieve itself of the ring strain.

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Conformations Of Cycloalkanes
The angles of regular pentagon (1080)
are very close to the tetrahedral angle
cyclopentane therefore, should be virtually
free of angle strain.
The angles of a regular hexagon
(1200) considered to be planar, are
somewhat larger than the tetrahedral
angle, as such, cyclohexane molecule
should have in it an angle strain of 10.50 .
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Chair Conformations of Cyclohexane

The chair form is the most stable
conformation of
cyclohexane, and
indeed, of nearly every derivative of
cyclohexane.
The chair conformation has 109.5
bond angles and all hydrogens are
staggered.
No angle strain and no torsional strain.
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