Nucleophiles and Nucleophilicity

Nucleophilicty vs. Basicity

All Nucleophiles act like Bases and vice-versa.

Base; Ability to accept proton

measured by thermodynamics
Nucleophilicity; ability to cause substitution
reaction (depends on reaction conditions)
measured by kinetics
 Nucleophilicty vs. Basicity

Type of Reaction Definition Strength

Nucleo Substitution; Causes a Rate of

phile R-X + Nu- -> substitution Reaction
R-Nu + X- reaction

Base H Proton Equilibria

Acceptor
C C + B-

+ BH
C C
 Guidelines for Determining Basicity
and Nucleophilicity
1. When the same nucleophilic atom is
compared; the anion is both more basic and
nucleophilic with respect to the neutral
molecule.

OH- More Basic & Nucleophilic

Than H2O
 Table 8.4 Nucleophilicity

Rank Nucleophile Relative

rate
good HO, RO 104

fair RCO2 103

weak H2O, ROH 1

When the attacking atom is the same (oxygen

in this case), nucleophilicity increases with
increasing basicity.
 Guidelines for Determining
Basicity and Nucleophilicity
2. If the comparison is made in the same
period; both nucleophilicity and basicity
increase going to the left.

NH2- > OH- >F-

More Basic and Nucleophilic

 Guidelines for Determining
Basicity and Nucleophilicity
3. If the comparison is made going down a
group; basicity increases going up while
nucleophilicity increases going down.

F- Cl- Br- I-

Increasing Nucleophilicity

Increasing Basicity
 Basicity Trend Down a Group

Acid Conjugate Base

HF; weak acid F-; strong conj base

HCl; strong acid Cl-; weak conj base

HBr; strong acid Br-; weak conj base

HI; strong acid I-; weak conj base

 Nucleophilicity Trend Down a Group

Solvation
small negative ions are highly
solvated in protic solvents

large negative ions are less solvated

As solvation increases; nucleophile

strength decreases
 Figure

Solvation of a chloride ion by ion-dipole attractive

forces with water. The negatively charged chloride
ion interacts with the positively polarized hydrogens
of water.
 Table Nucleophilicity

Rank Nucleophile Relative

rate
strong I- >105
good Br- 104
fair Cl-, F- 103

A tight solvent shell around an ion makes it

less reactive. Larger ions are less solvated than
smaller ones and are more nucleophilic.
 Guidelines for Determining Basicity
and Nucleophilicity

4. Steric hinderance decreases nucleophile

strength.
H

H C
H H H
- -
O C C O
H C H

H C H
H
H
H
 Table Nucleophilicity

Rank Nucleophile Relative

rate
strong I-, HS-, RS- >105
good Br-, HO-, 104
RO-, CN-, N3-
fair NH3, Cl-, F-, RCO2- 103
weak H2O, ROH 1
very weak RCO2H 10-2