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Left (II) : Not-stabilizing HOMO/HOMO (n/σ) interaction. Right (I) : Stailizing HOMO/LUMO (n/σ*) interaction

1) In an SN2 reaction, the nucleophile's HOMO (lone electron pair) interacts with the substrate's LUMO (antibonding C-L orbital). This HOMO/LUMO interaction leads to bond formation between the nucleophile and substrate. 2) A back-side attack, where the nucleophile approaches from the opposite side of the leaving group, allows for strong overlapping of the HOMO and LUMO orbitals. This back-side attack is preferred in SN2 reactions. 3) Side attacks lead to weaker HOMO/LUMO interactions due to smaller overlaps with the substrate's LUMO lobes. Front-side attacks are disfavored due to

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19 views

Left (II) : Not-stabilizing HOMO/HOMO (n/σ) interaction. Right (I) : Stailizing HOMO/LUMO (n/σ*) interaction

1) In an SN2 reaction, the nucleophile's HOMO (lone electron pair) interacts with the substrate's LUMO (antibonding C-L orbital). This HOMO/LUMO interaction leads to bond formation between the nucleophile and substrate. 2) A back-side attack, where the nucleophile approaches from the opposite side of the leaving group, allows for strong overlapping of the HOMO and LUMO orbitals. This back-side attack is preferred in SN2 reactions. 3) Side attacks lead to weaker HOMO/LUMO interactions due to smaller overlaps with the substrate's LUMO lobes. Front-side attacks are disfavored due to

Uploaded by

SOMA CHATTERJEE
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an SN 2  reaction, an occupied n orbital of the nucleophile (HOMO = highest occupied

moecular orbital; lone electron pair) interacts with the unoccupied, antibonding σ* orbital of the
substrate's C-L bond (LUMO = lowest unoccupied molecular orbital). As a result, a new bonding,
as well as a new antibonding molecular orbital are developed. The bonding molecular orbital has
a lower energy level than the initial n orbital of the nucleophile does. As only the two electrons of
the nucleophile have to be distributed among the new molecular orbitals, the antibonding
molecular orbital is not occupied. Therefore, the system is stabilized by the HOMO/LUMO
interaction. Thus, the HOMO/LUMO interaction leads to a bonding interaction between the
substrate and the nucleophile. If the nucleophile's n orbital interacts with the bonding, occupied σ
orbital of the C-L bond, the new antibonding molecular orbital would also have to be occupied.
The system would then not be stabilized by this HOMO/HOMO interaction. Thus, the
HOMO/HOMO interaction does not lead to a bonding interaction between the substrate and the
nucleophile.

Fig.2

HOMO/HOMO and HOMO/LUMO interactions in an SN2 reaction.

Left (II): Not-stabilizing HOMO/HOMO (n/σ) interaction. Right (I): Stailizing HOMO/LUMO
(n/σ*) interaction.

The strength of the HOMO/LUMO interaction depends considerably on the direction from which
the nucleophile approaches the substrate. Three borderline cases are conceivable:

Fig.3

Borderline cases of the nucleophile approach's direction.


 The nucleophile attacks the substrate along the C-L bonding axis from the opposite side
of L. This is a back-side attack.
 The nucleophile approaches the substrate along the C-L bonding axis from the side on
which L is found. This is called front-side attack.
 The nucleophile approaches the substrate perpendicularly to the C-L bonding axis. This
is a side attack.

Back-side attack
In a back-side attack of the nucleophile on the substrate, the following orbital interaction is
possible.

Fig.4

HOMO/LUMO interaction (n/σ*) in the back-side attack.

As one can see in the illustration above, the back-side attack enables the overlapping of the
nucleophilie's HOMO (n orbital, lone electron pair) with the substrate's LUMO (C-L σ*), in
particular with the larger lobe of the substrat's LUMO. If the nucleophile does not approach the
substrate exactly along the C-L bonding axis, the HOMO/LUMO interaction is weaker. To make a
long story short, the back-side attack leads to a strong bonding HOMO/LUMO interaction
between the nucleophile and the substrate. Therefore, the back-side attack actually occurs in

the SN 2  reaction.

Front-side and side attack

Fig.5
HOMO/LUMO interaction (n/σ*) in the side attack.

Due to the steric hindrance between the nucleophile and the leaving group, a front-side attack
that occurs right along the C-L bonding axis is particularly unfavourable. A side attack also has
several disadvantages.

 In the side attack, the minor overlapping of the nucleophile's LUMO with the smaller
orbital lobes of the substrate's LUMO (σ*), which are located between the carbon and the leaving
group, leads to a weaker interaction than in the back-side attack.
 In the side attack, one lobe of the nucleophile's HOMO overlaps with two small lobes of
the substrates LUMO (σ*). These small lobes of the LUMO have opposite signs in the
wavefunction, as the LUMO possesses a nodal plane between the carbon and the leaving goup.
Consequently, the overlapping of the nucleophile's HOMO with one of the small substrate's
LUMO lobes causes a bonding interaction, while the overlapping with the other small LUMO lobe
leads to an antibonding interaction. In summary it may be said, the HOMO/LUMO interactions in
the side attack do not produce bonding interactions between the substrate and the nucleophile.

Exercises

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