Having similar energies is not the only criterion for good interaction between two AOs. It also matters how the orbitals overlap. We have seen that p orbitals overlap better in an end-on fashion (forming a σ bond) than they do side-on (forming a π bond). Another factor is the size of the AOs. For best overlap, the orbitals should be the same size—a 2p orbital overlaps much better with another 2p orbital than it does with a 3p or 4p orbital.

A third factor is the symmetry of the orbitals—two AOs must have the appropriate symmetry to combine. Thus, a 2px orbital cannot combine with a 2p_y or 2p_z orbital since they are all perpendicular to each other (they are orthogonal). Depending on the alignment, there is either no overlap at all or any constructive overlap is cancelled out by equal amounts of destructive overlap. Likewise, an s orbital can overlap with a p orbital only end-on. Sideways overlap leads to equal amounts of bonding and antibonding interactions and no overall gain in energy.

مواضيع ذات صلة

The molecular orbitals of butadiene

Conjugation

Multiple double bonds not in a ring

Molecules with more than one C=C double bond Benzene has three strongly interacting double bonds

The structure of ethene (ethylene, CH2=CH2)

Bisulfite addition compounds

Acid and base catalysis of hemiacetal and hydrate formation

Ketones also form hemiacetals

Hemiacetals from reaction of alcohols with aldehydes and ketones

Addition of water to aldehydes and ketones

Addition of organometallic reagents to aldehydes and ketones

Nucleophilic attack by ‘hydride’ on aldehydes and ketones