16.2 : Stability of Conjugated Dienes

Introduction

A comparison of the enthalpies of hydrogenation of dienes reveals that conjugated dienes release less heat on hydrogenation, rendering them more stable than their nonconjugated analogs.

The two main factors contributing to the enhanced stability of conjugated systems are the delocalization of π electrons and the sp² hybridization of the carbons forming the single bonds.

Planar Conformers of Conjugated Dienes

Conjugated dienes adopt two planar configurations, s-cis and s-trans, where the unhybridized p orbitals are aligned parallel to each other, facilitating the delocalization of π electrons across the molecule. The s-cis and s-trans conformers of 1,3-butadiene are shown below.

The prefix “s” describes the orientation of the double bonds about the C–C single bond. The conformers undergo rapid internal conversion at room temperature via rotation around the central single bond. In the s-cis form, the two double bonds are on the same side of the single bond and have a dihedral angle of 0°. In s-trans, they are on the opposite sides with a dihedral angle of 180°. The s-cis conformer is less stable than the s-trans conformer due to the steric interaction between the two hydrogens as shown below.