3.

Charge on Nucleophile

Charged nucleophiles are better than neutral nucleophiles in the same

group.

HS- > H2S OH- > H2O NH2- > NH3

Table of Nucleophilic Strengths

Strong Nucleophile Moderate Weak

Strongest (CH3CH2)2P Br- F-

HS- NH3 H2O
I- CH3SCH3 CH3OH
(CH3CH2)2NH Cl-
CN- CH3CO2-
OH-
Weakest CH3O-
4. Bulky Nucleophiles

CH3CH2O- > (CH3)3CO-

Not Bulky Bulky
Unhindered Hindered

Alkoxides Ions

Effect of Leaving Group

N C X
N C + X

Leaving Group
 • The LG is usually displaced with a negative charge. LGs that best stabilize the
negative charge are best.

• Electronegative LGs, which polarize the C atom are also good.

• LGs should be polarizable to stabilize the Transition State

• In general, the weaker the base, the better the LG.

LG Rel. Reactivity pKa (conjugate acid)

O
H3C S O 60,000 -6.5
O
I- 30,000 -9.5 Weakest base
Br- 10,000 -9
F- 1 3.2
OH- ~0 15.7
NH2- ~0 35 Strongest
base
 O
H3C S O Symbolized as -OTs
O

tosylate group

O
H3C O S CH3
:N C
O

O
-O S CH3
:N C-CH3
O

Halogens as Leaving Groups

I- > Br- > Cl- > F-