Chapter 7:

Substitution
Reactions
SN2/SN1 Reaction Mechanism
δ-

Electronegativity of bromine: 2.96

Dipole moment

Electronegativity of carbon: 2.55

δ+

- Due to the difference in electronegativity between carbon and bromine, the central carbon is
electrophilic (lacking electron density)
- Orbital explanation: σ*CBr is very low in energy due to poor overlap between the carbon and
bromine orbitals, which makes it available to nucleophilic attack
SN2 Reaction Mechanism

- When the nucleophile attacks the electrophilic carbon, it must approach from the opposite side
as the leaving group
- This is called the “backside attack” (lol)
- NNuc puts electron pair into σ*C-LG and at the same time the LG takes the electron pair sitting in σ C-
LG and leaves the molecule as an anion
SN2 Reaction Mechanism

- Because the nucleophile MUST attack from the opposite side as the leaving group, there is
ALWAYS only one stereogenic product of an SN2 reaction (Walden inversion)
- If the nucleophile (entering group) and the leaving group have the same priority, the
stereocenter will flip from R to S or vice versa
- Some examples to elaborate
SN2 Reaction Mechanism
Example 1

S R

- Because the nucleophile MUST attack from the opposite side as the leaving group, there is
ALWAYS only one stereogenic product of an SN2 reaction (Walden inversion)
- If the nucleophile (entering group) and the leaving group have the same priority, the
stereocenter will flip from R to S or vice versa
- Some example to elaborate
Example 1 in 3D

I CH3

S R

H3C CH2CH3 CN CH2CH3

H H

-
CN:
SN2 Reaction Mechanism
Example 2

R
S

- Because the nucleophile MUST attack from the opposite side as the leaving group, there is
ALWAYS only one stereogenic product of an SN2 reaction (Walden inversion)
- If the nucleophile (entering group) and the leaving group have the same priority, the
stereocenter will flip from R to S or vice versa
- Some example to elaborate
Example 2 in 3D

CH2CH3 CH2CH3

-
CN: R S

H3C Br H3C H

H CN
SN2 Reaction Mechanism
Example 3

S
R

- Because the nucleophile MUST attack from the opposite side as the leaving group, there is
ALWAYS only one stereogenic product of an SN2 reaction (Walden inversion)
- If the nucleophile (entering group) and the leaving group have the same priority, the
stereocenter will flip from R to S or vice versa
SN2 Reaction Coordinate Diagram
Transition State
- Transition states are always energy maximum on reaction coordinate diagrams
- Think of them as the “steps” between each of your intermediates in a mechanism
- Example:

Breaking bond
Forming bond

Transition state Intermediate

Transition State
Full Mechanism
Intermediates are
energy minima (valleys)

Transition states are

energy maxima (hills)
SN2 Reaction Transition State
- How many intermediates exist in the SN2 mechanism?

There are no intermediates! That’s why we call it a one-step reaction

and the reaction coordinate diagram only has 1 hill (no valleys)
SN2 Reaction Rate
- The rate law of the SN2 mechanism depends on two species (that’s why SN2 is called a
bimolecular reaction)

- There is only one step, therefore both substances involved in that step must be apart of
the rate law: rate = k[S.M.][nuc]
- rate = k[C4H9Br][CN-]
SN1 Reaction Mechanism

- In the SN1 mechanism, first the leaving group leaves the S.M.
- This generates a carbocation, which is then quenched by the nucleophile
- Because carbocations are sp2 hybridized, the nucleophile can attack from either side
- This causes the product to be racemized (the product will be both R and R)
SN1 Reaction Mechanism

S
SN1 Reaction Coordinate
SN1 is a 2-step reaction, which step
is the rate determining step?
SN1 Reaction Coordinate
- Rate determining step = the
slowest step in a mechanism
- Forming the carbocation is the
most energetically demanding
step, and therefore it is the rate
determining step
- Because there is only one species
in this step (S.M), only the
starting material appears in the
rate law
- Rate = k [S.M.]
SN1 Reaction Coordinate
Differences Between SN1 and SN2
- SN2
- Bimolecular rate law that depends on both S.M. and nucleophile
- No intermediates, one transition state
- Needs a strong, not sterically-hindering nucleophile
- Carbon center needs to not to sterically hindered
- Walden inversion
- SN1
- Unimolecular rate law that depends only on the S.M.
- One intermediate (carbocation), two transition states
- Needs to be able to form a stable carbocation
- Does not need a strong nucleophile
- Racemized product
 When to use SN2 When to use SN1

Strong nucleophile Weak nucleophile

Polar aprotic, or non-polar aprotic solvent Polar protic solvent

1° or 2° carbon 2° or 3° carbon

The product consists of one stereoisomer The product is racemized

- Polar protic solvents can weaken the strength of the nucleophile through hydrogen bonds
- Polar aprotic and non-polar aprotic solvents can’t do this