Trends in Strength of Nucleophiles and Electrophiles

Nucleophiles (Nu:-) are electron donors. Nucleophiles are anions or neutral but never cations.
Electrophiles (E+) are electron acceptors. Electrophiles are usually cations or neutral but
occasionally are anions.
Study the following tables and note that
for nucleophiles with the same attacking atom (in the same column), the anion is a much
better nucleophile than the neutral atom
+
for electrophiles of the same kind (e.g., H2O and H3O ), the cation is a much better electrophile
than the neutral species.
+
some neutral molecules (like H2O) can be nucleophilic in the presence of a strong E
(e.g., H2O + HBr) and can be electrophilic in the presence of a strong Nu: (e.g., H2O + NH2-).
BH3

CH3+

NH4+

H3 O +

R-OH2+

HF

BH4-

:CH3-

:NH3

H2 O

R-OH

F-

NH2

OH
O

H3BO3

H2CO3

H2BO3

HCO3
CO3

R-O

-2

PH4+

H2 S

R-SH

HCl

:PH3

HS-

R-S-

Cl-

PH2-

S-2

HNO3

H3 O +

NO3

-2

E+ strength

Nu:- strength

H2 O
OH

E+ strength

HBr
Br

E+ strength

Nu:- strength

O-2

HCN

H3PO4

H2SO4

HClO3

CN-

H2PO4-

HSO4-

ClO3-

HPO4-2

SO4-2

E+ strength
Nu:- strength

PO4-3

Nucleophiles donate loosely held electrons. These are electrons (e.g., CH2=CH2) or non
bonded electrons (e.g., :NH3) but not electrons. Other examples include metals such as
Mg: and Na.
Some electrophiles have empty orbitals such as BH3 or AlCl3.
Other electrophiles produce an empty orbital in order to accept electrons from the Nu: -.
Strong Bronsted acids (protic acids such as HCl H+) are good examples.
Atoms with + charge are potential electrophiles, such as the C in a carbonyl group. It is +
and its weak bond to O can cleave to form an empty orbital (C +) . Similarly, a + C attached
to a good leaving group (e.g., -Br) can cleave a bond to form an empty orbital (C+).

ORGANIC CHEMISTRY INTRO

37

Study the following reactions.

nucleophiles and electrophiles.

Write products where they are not shown and identify

..
Cl
.. :

..
: Cl : - + H+
..

Na+

- ..

:O
..

Na+Cl-

acetone
lithium hydride
+

CH3

..
O
..

.. : O : Li+

: O:

Li+ H:-

CH3

CH3

CH3

..
Br
.. :

CH3
+

H3C

..
: Br: - + H+
..

: O:
CH3

..
O
..

H3C

CH3

..
O
..

CH3

CH3
C

..
O
+

CH3

H
H

H3C

CH3

C+
CH3

H3C

CH3

..
: Br: ..

H
sodium amide

: O:
CH3

.. :
O
..

..
: NH 2

..
Cl
.. :
H

H
C

Na +

+ H+

..
: Cl : - + H+
..

ORGANIC CHEMISTRY INTRO

C
H

+
C

H
H

37

Br