Neutrophiles and Electrophiles
Neutrophiles and Electrophiles
Neutrophiles 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+).
37
..
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+
..
C
H
+
C
H
H
37
Br