Frontier Molecular Orbital theoryApart from electrostatic interactions, the overlap between orbitals may favour the reaction between an electron donor and an electron acceptor. A high (in energy) lying occupied orbital in the donor may overlap with a low lying empty one in the acceptor, leading to a net stabilization.
The strength of the interaction is determined by:
- the energy difference between the two orbitals involved (the smaller the better).
- the amount of overlap between the orbitals (the larger the better).
These effects can account for the subtle differences that are found in facial selectivity, caused by
- steric effects which hinder overlap, or by
- asymmetry of a pi orbital, which favours overlap on that side where the orbital is larger.
Example: Diels-Alder reaction of fluorocyclopentadiene, which takes place on the side where the F resides. Sterically the other side would be preferred, so an electronic effect must play a role. We can investigate the orbital concerned, the HOMO of fluorocyclopentadiene, and other cyclopentadienes.