1.steric Effect

Steric Effect
1
Steric Effect
• The word “steric” is derived from ‘stereos’ meaning space. The amount of
space that a group of atoms takes is called the "steric bulk".
• Definition: “A steric effect is an effect (influence) on shape of molecule or

on a reaction's course or the relative rate of reaction caused by the space-
filling properties i.e. size or bulk of various parts (atoms or groups) of a
molecule attached at or near the reacting site.”
Explanation:
• Steric effects arise from a fact that each atom within a molecule occupies a
certain amount of space. The electrons of the near atoms want to stay away
from each other. When two or more atoms or groups get too close, this costs
energy. It is so because the electronic cloud surrounding each atom repel
each other. This repulsion makes the molecule unstable and also affect the
molecule’s preferred shape (conformation) and reactivity.
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• Note: Steric effects are usually smaller than electronic effects (like resonance
effect, electromeric effect, inductive effect etc.).
Types of Steric Effects: Common steric effects includes Steric
hindrance and Van der Waals strain (van der Waals repulsion).
[1]. Steric Hindrance: “Steric hindrance is a decrease in reactivity of

compounds resulting from the presence of bulky groups at the site of a
reaction.”
• Steric hindrance occurs when the spatial arrangement and large size
of atoms or groups within (at or near a reacting site of) a molecule
hinders or retards a chemical reaction that is normally observed in
related molecules with smaller groups.
• A bulky group like -CH3 , –C2H5 , –C6H5 , etc. can block a position.
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• Example - 1: In an SN2 reaction increasing the number and/or size of
alkyl groups on the carbon bearing the leaving group (LG) causes
more steric hindrance to backside attack in the transition state,
leading to slower reaction rates.
• The SN2 reaction is fastest with unhindered halides.
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Explanation:
• The carbon atom in bromomethane is readily accessible resulting in a
fast SN2 reaction.
• The carbon atoms in bromoethane (primary), 2-bromopropane
(secondary), and 2-bromo-2-methylpropane (tertiary) are successively
more hindered, resulting in successively slower SN2 reactions.
• Methyl group occupies significant space, so when hydroxide ion
approaches the central carbon atom, methyl group starts repelling the
hydroxide ion.
• Presence of two methyl groups makes it more tough. In the case of 5
three methyl groups, reaction hardly occurs. So one can say that methyl
group has steric effect on the hydroxide ion.
• Example No. 2: A substitution reaction of 1,5-dibromo-5-methylhexane with
NaI. Note that substitution takes at carbon-1 and not at carbon-5 due to
steric hinderance.
• Example No. 3: A substitution reaction on a halide by a hydroxide does not

work in the case given below because of steric hindrance. The second figure
represents the same reaction, with spheres replacing the alkyl groups.
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• Magnitude of Steric Hindrance: It is proportional to the size and number of
substituents present in the vicinity of reaction site.
• Steric Hindrance as a Useful Tool: It is often exploited by chemists to change

the reactivity pattern of a molecule by:
1. stopping unwanted side-reactions (steric protection) or

2. by leading to a preference for one stereochemical reaction course.
[2]. Steric Strain/Van der Waals repulsion:

• “The energetically unfavorable (repulsive) force resulting from the
interaction of the bonded electrons of one molecule and those of
another, or of the nuclei of one molecule with those of another is called
Van der Waals repulsion.”
OR
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• “Steric strain is an increase in increase in potential energy of a molecule
due to repulsion between electrons when big groups (occupying a large
volume) are forced close to each other.”
• It is also called Van der Waals strain and is related to steric hindrance.
• One of the most common forms of this strain is eclipsing hydrogen, in

alkanes.
• Example: The ethane molecule in the eclipsed conformation is said to suffer
from torsional strain. (An eclipsed conformation is a conformation in which
two substituents X and Y on adjacent atoms A, B are in closest proximity,
implying that the torsion angle X–A–B–Y is 0°).
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Significance of Steric Effect
1. Steric effects affect the rates and activation energies of most chemical
reactions to varying degrees.
2. Steric effects often dictate reaction pathways in organic synthesis

because there are fewer configurations in which molecules can collide
and successfully react.
3. Steric effect affects different properties of molecules, like acidity,
basicity and general reactivity.
4. 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.
5. In biological systems where everything occurs in the level of angstroms

and in a very precise manner, steric effects even due to tiny H - atoms 9
can result in the improper folding of proteins, leading to serious
diseases like Alzheimer’s Disease (a type of dementia that causes
problems with memory, thinking and behavior).
6. Steric clashes can lead to improper DNA replication resulting is
destruction of genetic information and hence to a large number of
genetic diseases including cancer.
7. In pharmacology, steric effects determine how and at what rate a

drug will interact with its target bio-molecules.
8. Steric hindrance between adjacent groups can also restrict torsional

bond angles and so it can also affect the finally adapted molecular
shape.
9. Steric effects are also important in aromatic substitutions.
• Substitution does not occur to an appreciable extent between meta

substituents if another position is open.
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• Example: A good example of this effect can be seen in the nitration of
m-bromochlorobenzene:
• Only 1% of the mononitro product has the nitro group between the
bromine and chlorine.
[10]. Steric strain inhibits the resonance. This phenomenon is known

as steric inhibitions of resonance.
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• Due to bulky groups attached to a benzene derivative compound, the
group attached to benzene goes out of plane and hence resonance is
• Example: If we compare basicities of o-Toluidine and aniline, o-
Toluidine is more basic than aniline.
• Due to the bulky methyl group present on o-Toluidine, because

electronic cloud of the methyl group repels the lone pair on nitrogen
due to which it becomes difficult for this lone pair of electrons to be
pulled into the ring.
• So there is inhibition of resonance which increases the availability of

nitrogen's lone pair for donation. 12
• Hence, we can say o-Toluidine is more basic than aniline(as nitrogen

Example:
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Steric Effect

• Definition: “A steric effect is an effect (influence) on shape of molecule or

[1]. Steric Hindrance: “Steric hindrance is a decrease in reactivity of

• Example No. 3: A substitution reaction on a halide by a hydroxide does not

• Steric Hindrance as a Useful Tool: It is often exploited by chemists to change

1. stopping unwanted side-reactions (steric protection) or

[2]. Steric Strain/Van der Waals repulsion:

• One of the most common forms of this strain is eclipsing hydrogen, in

2. Steric effects often dictate reaction pathways in organic synthesis

4. In biochemistry, steric effects are often exploited in naturally occurring

5. In biological systems where everything occurs in the level of angstroms

7. In pharmacology, steric effects determine how and at what rate a

8. Steric hindrance between adjacent groups can also restrict torsional

9. Steric effects are also important in aromatic substitutions.

• Substitution does not occur to an appreciable extent between meta

[10]. Steric strain inhibits the resonance. This phenomenon is known

• Due to the bulky methyl group present on o-Toluidine, because

• So there is inhibition of resonance which increases the availability of

• Hence, we can say o-Toluidine is more basic than aniline(as nitrogen

Thank You Very Much 

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