Scribd
Upload
64 views

Conform Analysis

Conformational analysis is the study of the energetics of different conformations of organic molecules. Conformations are structures related by bond rotations that are usually interconvertible at room temperature. The barrier to rotation is the energy required to twist a bond into a specific conformation. For ethane and propane, the staggered conformation is more stable than the eclipsed conformation due to hyperconjugation and steric repulsion respectively. The eclipsed interactions of H/H, H/Me and Me/Me provide different stabilization energies.

Uploaded by

hugo200887
Copyright
© Attribution Non-Commercial (BY-NC)
Available Formats
Download as PDF, TXT or read online on Scribd
64 views

Conform Analysis

Conformational analysis is the study of the energetics of different conformations of organic molecules. Conformations are structures related by bond rotations that are usually interconvertible at room temperature. The barrier to rotation is the energy required to twist a bond into a specific conformation. For ethane and propane, the staggered conformation is more stable than the eclipsed conformation due to hyperconjugation and steric repulsion respectively. The eclipsed interactions of H/H, H/Me and Me/Me provide different stabilization energies.

Uploaded by

hugo200887
Copyright
© Attribution Non-Commercial (BY-NC)
Available Formats
Download as PDF, TXT or read online on Scribd
You are on page 1/ 3

Conformational Analysis: The Fundamentals

conformational analysis: study of the energetics of different conformations

conformations: structures related by bond rotations; usually interconvertible at RT

conformer: conformation at potential energy minima

Newman Projections
H H back carbon
H H H (circle)
H H
H H H front carbon
H (point)
H
q = dihedral angle

Barrier to Rotation: torsional energy; energy required to twist a bond into a specific conformation;
Barrier to Rotation = Erel (highest energy conformer) – Erel (lowest energy conformer)
Ethane Propane
H HH H HH
H H H H
H Me
H H H H H H H H
H H Me H
staggered eclipsed staggered eclipsed
q = 60° q = 0° q = 60° q = 0°
Erel = 0 kcal/mol Erel = 3.0 kcal/mol Erel = 0 kcal/mol Erel = 1.4 kcal/mol

Barrier to Rotation = 3.0 – 0 = 3.0 kcal/mol Barrier to Rotation = 1.4 – 0 = 1.4 kcal/mol

H/H-eclipsing = 1.0 kcal/mol H/Me-eclipsing = 1.4 kcal/mol

• One explanation for the lower energy of staggered ethane is that the staggered conformer is
stabilized by hyperconjugation (stabilizing overlap between sCH and s*CH orbitals that does
not occur in the eclipsed conformer).

H H H H
sCH sCH
H H
H H H2C H H H H
H CH2 s*CH
H s*CH H
H H H H H
Hyperconjugation (staggered) (good overlap) eclipsed
(poor overlap)
• The barrier to rotation for propane is slightly higher than ethane because there is electron
repulsion between the methyl group and the eclipsed hydrogen atom in the eclipsed conformer.
Butane
MeMe Me HMe Me
H Me H H
H Me
H H H H H H H H
H H H Me
fully eclipsed gauche eclipsed anti
(eclipsed) (staggered) (eclipsed) (staggered)
qMe/Me = 0° qMe/Me = 60° qMe/Me = 120° qMe/Me = 180°
Erel = 4.6 kcal/mol Erel = 0.9 kcal/mol Erel = 3.8 kcal/mol Erel = 0 kcal/mol

Barrier to Rotation = 4.6 – 0 = 4.6 kcal/mol

Me/Me-eclipsing = 2.6 kcal/mol*

Gauche Butane Interaction (gbi) = 0.9 kcal/mol

The Me/Me-eclipsing interaction is said to be worth


Numbers to Remember various values in other sources. A Me/Me-eclipsing
interaction is significantly higher than an H/H- or
H/Me-eclipsing interaction because the hydrogens
H/H-eclipsing = 1.0 kcal/mol on the two methyl groups can actually bump into
each other (steric strain).
H/Me-eclipsing = 1.4 kcal/mol

Me/Me-eclipsing = 2.6 kcal/mol* H H H


H H H H H H
Gauche Butane (gbi) = 0.9 kcal/mol H H H
H/H H/Me Me/Me

You might also like