Steric effects are nonbonding interactions that influence the shape (conformation) and reactivity of ions and molecules. Steric effects complement electronic effects, which usually dictate shape and reactivity. Steric effects result from repulsive forces between overlapping electron clouds. Steric effects are widely exploited in applied and academic chemistry.
Steric hindrance is a consequence of steric effects. Steric hindrance is the slowing of chemical reactions due to steric bulk. It is usually manifested in intermolecular reactions, whereas discussion of steric effects often focus on intramolecular interactions. Steric hindrance is often exploited to control selectivity, such as slowing unwanted side-reactions.
Steric hindrance between adjacent groups can also affects torsional bond angles. Steric hindrance is responsible for the observed shape of rotaxanes and the low rates of racemization of 2,2'-disubstituted biphenyl and binaphthyl derivatives.
Because steric effects have profound impact on properties, the steric properties of substituents have been assessed by numerous methods.
Relative rates of chemical reactions provide useful insights into the effects of the steric bulk of substituents. Under standard conditions methyl bromide solvolyzes 107 faster than does neopentyl bromide. The difference reflects the inhibition of attack on the compound with the sterically bulky (CH3)3C group.
A values provide another measure of the bulk of substituents. A values are derived from equilibrium measurements of monosubstituted cyclohexanes. The extent that a substituent favors the equatorial position gives a measure of its bulk.
Ceiling temperature () is a measure of the steric properties of the monomers that comprise a polymer. is the temperature where the rate of polymerization and depolymerization are equal. Sterically hindered monomers give polymers with low 's, which are usually not useful.