Steric effects
- See also: intramolecular forces
Steric effects arise from the fact that each atom within a molecule occupies a certain amount of space. If atoms are brought too close together, there is an associated cost in energy due to overlapping electron clouds (Pauli or Born repulsion), and this may affect the molecule's preferred shape (conformation) and reactivity.
Types of steric effects
Steric hindrance
Steric hindrance occurs when the large size of groups within a molecule prevents chemical reactions that are observed in related molecules with smaller groups. Although steric hindrance is sometimes a problem (it prevents SN2 reactions with tertiary substrates from taking place), it can also be a very useful tool, and is often exploited by chemists to change the reactivity pattern of a molecule by stopping unwanted side-reactions (steric protection) or by leading to a preference for one stereochemical reaction course as in diastereoselectivity. Steric hindrance between adjacent groups can also restrict torsional bond angles. However, hyperconjugation has been suggested as an explanation for the preference of the staggered conformation of ethane because the steric hindrance of the small hydrogen atom is far too small.[1][2] This is the effect responsible for the observed shape of rotaxanes.
When a Lewis acid and Lewis base cannot combine due to steric hindrance, they are said to form a frustrated Lewis pair.
Other types of steric effects
Steric shielding occurs when a charged group on a molecule is seemingly weakened or spatially shielded by less charged (or oppositely charged) atoms, including counterions in solution (Debye shielding). In some cases, for an atom to interact with sterically shielded atoms, it would have to approach from a vicinity where there is less shielding, thus controlling where and from what direction a molecular interaction can take place.
Steric attraction occurs when molecules have shapes or geometries that are optimized for interaction with one another. In these cases molecules will react with each other most often in specific arrangements.
Chain crossing: A chain, ring, or a set of rings cannot change from one conformation to another if it would require a chain (or ring - a ring is a cyclic chain) to pass through itself or another chain. This is responsible for the shape of catenanes and molecular knots.
Steric repulsions between different parts of molecular system were found of key importance to govern the direction of transition metal mediated transformations and catalysis. Steric effect can even induce a mechanism switch in the catalytic reaction.[4]
Steric effects vs. electronic effects
The structure, properties, and reactivity of a molecule is dependent on straight forward bonding interactions including covalent bonds, ionic bonds, hydrogen bonds and lesser forms of bonding. This bonding supplies a basic molecular skeleton that is modified by repulsive forces. These repulsive forces include the steric interactions described above. Basic bonding and steric are at times insufficient to explain many structures, properties, and reactivity. Thus steric effects are often contrasted and complemented by electronic effects implying the influence of effects such as induction, conjunction, orbital symmetry, electrostatic interactions, and spin state. There are more esoteric electronic effects but these are among the most important when considering structure and chemical reactivity.
A special computational procedure was developed to separate electronic and steric effects of an arbitrary group in the molecule and to reveal their influence on structure and reactivity.[5]
Significance
Understanding steric effects is critical to chemistry, biochemistry and pharmacology. In chemistry, steric effects are nearly universal and affect the rates and energies of most chemical reactions to varying degrees. In biochemistry, steric effects are often exploited in naturally occurring molecules such as enzymes, where the catalytic site may be buried within a large protein structure. In pharmacology, steric effects determine how and at what rate a drug will interact with its target bio-molecules.
Note the organic chemical example of Stereochemistry of ketonization of enols and enolates where diastereoselectivity results from steric hindrance.
See also
- Collision theory
- Reaction rate acceleration as result of steric hindrance in the Thorpe-Ingold effect
- Sterically induced reduction
References
- ^ Pophristic, Vojislava; Goodman, Lionel (2001). "Hyperconjugation not steric repulsion leads to the staggered structure of ethane". Nature. 411 (6837): 565–8. doi:10.1038/35079036. PMID 11385566.
- ^ Weinhold, Frank (2001). "Chemistry. A new twist on molecular shape". Nature. 411 (6837): 539–41. doi:10.1038/35079225. PMID 11385553.
- ^ Gait, Michael (1984). Oligonucleotide synthesis: a practical approach. Oxford: IRL Press. ISBN 0-904147-74-6.
- ^ Ananikov, Valentin P.; Szilagyi, Robert; Morokuma, Keiji; Musaev, Djamaladdin G. (2005). "Can Steric Effects Induce the Mechanism Switch in the Rhodium-Catalyzed Imine Boration Reaction? A Density Functional and ONIOM Study". Organometallics. 24 (8): 1938. doi:10.1021/om049156o.
- ^ Ananikov, Valentine P.; Musaev, Djamaladdin G.; Morokuma, Keiji (2007). "Critical Effect of Phosphane Ligands on the Mechanism of Carbon–Carbon Bond Formation Involving Palladium(II) Complexes: A Theoretical Investigation of Reductive Elimination from Square-Planar and T-Shaped Species". European Journal of Inorganic Chemistry. 2007 (34): 5390. doi:10.1002/ejic.200700850.
External links
- www
.chem .swin .edu .au /modules /mod4 /qsarwebp4 .html - Steric A Program to Calculate the Steric Size of Molecules