Bond Breaking and Making in

Nucleophilic Substitution Mechanisms

But what is the order of bond making and bond

breaking?
In theory, there are three possibilities.
• Bond making and breaking occur at the same
time.
• Bond breaking occurs first.
• Bond making occurs first.
 Nucleophilic Substitution Mechanism –
Concerted
1. Bond making and bond breaking occur at the same
time.

• The mechanism is comprised of one step.

• In such a bimolecular reaction, the rate depends upon
the concentration of both reactants.
• The rate equation is second order.
 Nucleophilic Substitution
Mechanisms– Bond Breaking First
2. Bond breaking occurs before bond making.

• The mechanism has two steps and a carbocation is formed

as an intermediate.
• The first step is rate-determining.
• The rate depends on the concentration of RX only.
• The rate equation is first order.
3
 Nucleophilic Substitution
Mechanisms– Bond Making First
3. Bond making occurs before bond breaking.

• This mechanism has an inherent problem.

• The intermediate generated in the first step has 10 electrons
around carbon, violating the octet rule.
• Because two other mechanistic possibilities do not violate a
fundamental rule, this last possibility can be disregarded. 4
 Kinetics and Mechanisms
Consider reaction 1 below:

• Kinetic data show that the rate of reaction 1 depends on the

concentration of both reactants, which suggests a bimolecular
reaction with a one-step mechanism.
• This is an example of an SN2 (substitution nucleophilic
bimolecular) mechanism.
5
 Kinetics and Mechanisms
Consider reaction 2 below:

• Kinetic data show that the rate of reaction 2 depends on the

concentration of only the alkyl halide.
• This suggests a two-step mechanism in which the rate-
determining step involves the alkyl halide only.
• This is an example of an SN1 (substitution nucleophilic
unimolecular) mechanism. 6
The SN2 Mechanism
• An SN2 reaction is a type of chemical reaction where a
nucleophile replaces a leaving group on an
electrophile in a single step.
• The term "SN2" stands for "substitution nucleophilic
bimolecular”. Generally,
Energy Diagrams for SN2 Reactions

8
 Transition States of SN2 Reactions
• The transition state always has partial bonds to the nucleophile and
the leaving group.
• There can also be partial charges on the nucleophile and/or leaving
group.

Figure 7.9

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TASK 5
TASK 6
• If the carbon atom at the site of substitution is a chiral
centre, the SN2 mechanism results in stereochemical
inversion.
• This means that the substitution product has the opposite
absolute configuration to the initial substrate.
• Inversion occurs because the nucleophile attacks from the
opposite side from the leaving group.
• In the transition state, the nucleophile and leaving group
are 180° away from each other, and the other three groups
around carbon occupy a plane, as illustrated in Figure 7.9.
 Inversion in SN2 Reactions
• The bond to the nucleophile in the product is always on the opposite side
relative to the bond of the leaving group in the starting material.
• This is called backside attack.
• This results in inversion of configuration at a stereogenic center.

13
TASK 7

14
 Substrate Reactivity in SN2 Reactions
• As the number of R groups on the carbon with the leaving group
increases, the rate of an SN2 reaction decreases.

• Methyl and 1° alkyl halides undergo SN2 reactions with ease.

• 2° Alkyl halides react more slowly.
• 3° Alkyl halides do not undergo SN2 reactions due to steric
effects.
• Bulky R groups near the reaction site make nucleophilic
attack from the backside more difficult, slowing the reaction
rate. 15
Energy Diagrams for SN2 Reactions
• The higher the Ea, the slower the reaction rate.
• Thus, any factor that increases Ea decreases the reaction rate.
Figure 7.12

16
 Effect of Sterics on Rate of SN2 Reactions
• Increasing the number of R groups on the carbon with the
leaving group increases crowding in the transition state,
thereby decreasing the reaction rate.
• The SN2 reaction is fastest with unhindered halides.

17
TASK 8

18
Characteristics of the SN2 Mechanism

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 The SN1 Mechanism
• In an SN1 reaction, the bond between the carbon atom and the
leaving group is broken first. This is known as dissociation.
• The term "SN1" stands for "substitution
nucleophilic unimolecular”.
• This step produces an intermediate that has a carbon atom
with a formal positive charge, known as a carbocation. A
carbocation is highly electrophilic.
• The formation of a carbocation intermediate is most likely to
occur if the carbocation is stabilized by the structure of the
substrate.
• The second step in this mechanism is the formation of a
covalent bond between the nucleophile and the carbocation.
• The dissociation step is much slower
than the second step. Thus, the first step
is rate limiting and the reaction is first
order as it depends only on the
concentration of the substrate.
• An example of an SN1 mechanism is the
reaction between 2-chloro-2-
methylpropane and iodide ions:
TASK 9
 Stereochemistry and Racemization in SN1
Mechanism
• Loss of the leaving group in Step [1] generates a planar carbocation
that is achiral.
• In Step [2], attack of the nucleophile can occur on either side to afford
two products which are a pair of enantiomers.
• Because there is no preference for nucleophilic attack from either
direction, an equal amount of the two enantiomers is formed—a
racemic mixture.
• This process is called racemization.

25
 Substrate Reactivity in SN1 Reactions
• The rate of an SN1 reaction is affected by the type of alkyl halide
involved.

• This trend is exactly opposite to that observed in SN2

reactions.
26
 Carbocation Stability
• The effect of the type of alkyl halide on S N1 reaction rates can be
explained by considering carbocation stability.
• Carbocations are classified as primary (1°), secondary (2°), or
tertiary (3°), based on the number of R groups bonded to the
charged carbon atom.
• As the number of R groups increases, carbocation stability
increases.

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Characteristics of the SN1 Mechanism

28
 Predicting the Mechanism of Nucleophilic
Substitutions Reactions
• Four factors are relevant in predicting whether a
given reaction is likely to proceed by an SN1 or an SN2
mechanism:
• The alkyl halide—CH3X, RCH2X, R2CHX or R3CX

• The nucleophile—strong or weak

• The leaving group—good or poor

• The solvent—protic or aprotic 29

29
 Nature of the Alkyl Halide
• The most important factor is the identity of the alkyl halide.

30
 Effect of the Nucleophile
• Strong nucleophiles (which usually bear a negative charge)
present in high concentrations favor S N2 reactions.
• Weak nucleophiles, such as H2O and ROH favor SN1 reactions by
decreasing the rate of any competing S N2 reaction.
• Consider what happens when the 2° alkyl halide A, which can
react by either mechanism, is treated with either the strong
nucleophile HO¯ or the weak nucleophile H2O.

31
 Predicting SN1 or an SN2–Nucleophile
• The strong nucleophile favors an SN2 mechanism.

• The weak nucleophile favors an SN1 mechanism.

32
 Effect of Leaving Groups
• A better leaving group increases the rate of both SN1 and SN2
reactions.

33
 Effect of Solvent
• Polar protic solvents like H2O and ROH favor SN1 reactions because
the ionic intermediates (both cations and anions) are stabilized by
solvation. Examples incude;

• Polar aprotic solvents favor SN2 reactions because nucleophiles

are not well solvated, and therefore, are more nucleophilic.
Examples include;

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Predicting SN1 or an SN2–Summary

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REVIEW QUESTIONS

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