steric effect

https://doi.org/10.1351/goldbook.S05997
The effect on a chemical or physical property (structure, rate or @E02177@) upon introduction of @S06076@ having different steric requirements. The steric effect in a reaction is ascribed to the difference in steric energy between, on the one hand, reactants and, on the other hand, a @T06468@ (or products). A steric effect on a rate process may result in a rate increase ('steric @A00051@') or a decrease ('steric retardation'). (The adjective 'steric' is not to be confused with stereochemical.) Steric effects arise from contributions ascribed to @S06037@ as the sum of (1) non-bonded repulsions, (2) bond @A00349@ and (3) bond stretches or compressions. For the purpose of @C01346@ or @L03551@ various scales of steric parameters have been proposed, notably @A00012@, Taft's \(E_{\text{s}}\) and Charton's \(\nu \) scales. In a reactant molecule RY and an appropriate reference molecule RoY , the 'primary steric effect' of R is the direct result of differences in compressions which occur because R differs from Ro in the vicinity of the reaction centre Y . A 'secondary steric effect' involves the differential moderation of electron @D01583@ by non-bonded compressions. Some authors make a distinction between 'steric' effects attributed to van der Waals repulsions alone, and '@S06037@' effects, attributed to deviations of bond angles from 'ideal' values.
See:
'A' value
,
correlation analysis
,
linear free-energy relation
,
strain
,
substituent atom (group)
,
Taft equation
,
transition state
,
van der Waals forces
Source:
PAC, 1994, 66, 1077. (Glossary of terms used in physical organic chemistry (IUPAC Recommendations 1994)) on page 1168 [Terms] [Paper]