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Nucleophiles and Nucleophilicity

Nucleophiles can act as both bases and in substitution reactions. Nucleophilicity refers to the ability to participate in substitution reactions and is measured kinetically, while basicity refers to the ability to accept protons and is measured thermodynamically. There are several guidelines for comparing nucleophilicity and basicity: 1) anions are more nucleophilic and basic than the corresponding neutral molecule, 2) within a period both increase going left, 3) within a group basicity increases up but nucleophilicity increases down due to solvation effects, and 4) steric hindrance decreases nucleophilicity.

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86 views13 pages

Nucleophiles and Nucleophilicity

Nucleophiles can act as both bases and in substitution reactions. Nucleophilicity refers to the ability to participate in substitution reactions and is measured kinetically, while basicity refers to the ability to accept protons and is measured thermodynamically. There are several guidelines for comparing nucleophilicity and basicity: 1) anions are more nucleophilic and basic than the corresponding neutral molecule, 2) within a period both increase going left, 3) within a group basicity increases up but nucleophilicity increases down due to solvation effects, and 4) steric hindrance decreases nucleophilicity.

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GrenlyKereh
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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

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