Chemists
commonly
use
the
following
types
of
arrows:


• A
double‐headed
arrow
links
two
resonance
structures



 

• Two
half‐headed
arrows
indicate
an
equilibrium



 

• A
curved
arrow
indicates
the
movement
of
an
electron
pair
in
the
direction
of
the

arrowhead


g
or

 

• A
curved
half‐headed
arrow
indicates
the
movement
of
a
single
electron
in
the

direction
of
the
arrowhead
 u.
s4
va


 



an

RESONANCE:
sometimes
all
the
properties
of
a
molecule
can’t
be
represented
by
a
single

.c

structure
but
by
two
or
more
structures.
These
contributing
structures
are
known
as

w

canonical
forms
or
resonating
structures.
The
actual
molecule
is
represented
by
a
hybrid
of

w

these
canonical
forms.
Resonating
structures
are
not
the
structures
for
the
actual
molecule
op

w

ion;
they
exist
only
on
paper.
Resonance
is
a
hypothetical
concept
used
to
explain
the
extra

stability
of
some
molecules
or
ions.



Rules
for
writing
the
resonance
structures:

• All
the
canonical
forms
must
be
proper
Lewis
structures.
For
instance,
none
of
them

may
have
a
carbon
with
five
bonds.

• The
positions
of
the
nuclei
must
be
the
same
in
all
the
structures.
We
are
allowed
only

to
move
electrons
and
no
atom
should
be
displaced
from
its
position.


• All
atoms
taking
part
in
the
resonance,
that
is,
covered
by
delocalized
electrons,
must

lie
in
a
plane
or
nearly
so.
This,
of
course,
does
not
apply
to
atoms
that
have
the
same

 bonding
in
all
the
canonical
forms.
The
reason
for
planarity
is
maximum
overlap
of
the

p
orbitals.

• All
canonical
forms
must
have
the
same
number
of
unpaired
electrons.
Thus
CH2—
CH=CH—CH2
is
not
a
valid
canonical
form
for
butadiene.

• The
energy
of
the
actual
molecule
is
lower
than
that
of
any
form,
obviously.
Therefore,

delocalization
is
a
stabilizing
phenomenon.

• All
canonical
forms
do
not
contribute
equally
to
the
true
molecule.
Each
form

contributes
in
proportion
to
its
stability,
the
most
stable
form
contributing
most.

Equivalent
canonical
forms,
such
as
1
and
2,
contribute
equally.
The
greater
the

number
of
significant
structures
that
can
be
written
and
the
more
nearly
equal
they

are,
the
greater
the
resonance
energy,
other
things
being
equal.

• Structures
with
more
covalent
bonds
are
ordinarily
more
stable
than
those
with
fewer.



g
• Stability
is
decreased
by
an
increase
in
charge
separation.
Structures
with
formal


or
charges
are
less
stable
than
uncharged
structures.
Structures
with
more
than
two


u.
formal
charges
usually
contribute
very
little.
An
especially
unfavorable
type
of

s4
structure
is
one
with
two
like
charges
on
adjacent
atoms.

• Structures
that
carry
a
negative
charge
on
a
more
electronegative
atom
are
more

va

stable
than
those
in
which
the
charge
is
on
a
less
electronegative
atom.

an

Drawing
Resonance
Structures

.c

Seeing
Cations
Next
to
a
Double
Bond,
Triple
Bond,
or
Lone

w

Pair

w



w

One
pattern
that
indicates
that
more
than
one
resonance
structure
exists
for
a
molecule
is
a

cation
situated
next
to
a
double
bond,
a
triple
bond,
or
a
lone
pair.
A
cation
is
organic‐speak

for
a
positively
charged
atom;
when
a
cation
is
located
on
a
carbon
atom,
the
charge
is
often

specifically
referred
to
as
a
carbocation.



To
draw
alternative
resonance
structures
matching
this
pattern,
follow
these
steps:



1.

 Push
the
electrons
from
the
double
bond,
triple
bond,
or
lone
pair
toward
the


 charged
atom.


 Draw
an
arrow
from
the
electrons
you’re
moving
toward
the
positively
charged

 atom.


 
 

2.

 Move
the
arrows
correctly.


 Arrows
represent
the
movement
of
two
electrons
from
where
they
started
to
where


 they’re
going,
so
make
sure
the
arrow
starts
in
one
of
these
places:



• At
the
double
or
triple
bond,
to
indicate
the
movement
of
these
pi
electrons

• From
the
lone
pair
of
electrons




 Then
make
the
arrow
point
between
the
positively
charged
atom
and
the
closest


 adjacent
atom
to
indicate
that
these
two
electrons
are
being
moved
here
in
order
to


g

 form
a
new
double
bond.


or

 

3.

 u.
Draw
the
resonance
structure
showing
the
new
double
bond,
and
check
your

s4

 charges.



va


 The
positive
charge
should’ve
moved
either
to
one
of
the
original
double‐bond
or

an


 triple‐bond
atoms
(if
you
moved
a
double
or
triple
bond)
or
to
the
atom
that
originally


 contained
the
lone
pair
(if
you
moved
a
lone
pair).

.c
w
w
w





Q.
Draw
the
other
resonance
structures
for
the
following
cationic
molecule
by
arrow

pushing.
After
you’ve
drawn
all
the
resonance
structures,
draw
what
the
actual
structure
of

the
molecule
looks
like,
including
charges.










Answer:










Q.
Draw
the
resonance
structure
for
the
following
molecules
by
using
arrow‐pushing.

After
you’ve
drawn
the
resonance
structure,
sketch
what
the
actual
structure
looks
like,

including
charges.





 
 
 
 
 


g

 (a)
 
 
 
 (b)
 
 







(c)

 






 






(d)


or

 


u.
s4

 
 


 (e)
 
 
 
 (f)

va



Answer:



an
.c
w





w



w















 








Pushing
Lone
Pairs
Next
to
a
Double
or
Triple
Bond



Another
pattern
you
see
that
indicates
that
a
molecule
can
be
described
by
more
than
one

Lewis
structure
is
an
atom
with
a
lone
pair
directly
attached
to
a
double
bond
or
triple
bond.




g
To
draw
alternative
resonance
structures
matching
this
pattern,
follow
these
steps:


or


1.

 u.
Push
the
electrons
from
the
lone
pair
toward
the
double
bond
or
triple
bond.

s4

 To
accomplish
this
electron
pushing,
draw
an
arrow
from
the
lone‐pair
electrons


 pointing
toward
the
center
of
the
adjacent
bond.
This
move
indicates
that
you’re

va


 using
the
lone
pair
to
form
a
new
double
bond.

an



2.

 Move
the
double­
or
triple
bond
pi
electrons
onto
the
farthest
atom
as
a
lone

.c


 pair.

w


 Draw
an
arrow
starting
from
the
middle
of
the
double
or
triple
bond
and
move
the

w


 electrons
onto
the
farthest
atom
in
the
double
or
triple
bond
by
pointing
the
head
of

w


 the
arrow
to
this
atom.



 
 

3.

 Draw
the
resonance
structure
and
check
your
charges.


 The
atom
with
the
initial
lone
pair
becomes
one
charge
more
positive
in
the


 resonance
structure
than
what
it
started
with,
and
the
atom
that
received
the


 double‐
or
triple
bond
electrons
as
a
lone
pair
becomes
one
charge
more
negative


 than
what
it
started
with.



Q.
Draw
the
other
resonance
structures
for
the
following
molecules
by
arrow‐pushing.



 
 
 
 


 




(a)
 
 














(b)
 
 
 









(c)





 
 


 (d)
 
 
 
 (e)



Answers:









g
or

 u.
s4


va



an



.c
w





w
w







Pushing
Double
or
Triple
Bonds
Containing
an

Electronegative
Atom



If
a
double
or
triple
bond
contains
an
electronegative
atom,
such
as
oxygen
or
nitrogen,
you

can
draw
a
resonance
structure
in
which
the
double
bond
moves
onto
the
electronegative

atom
as
a
lone
pair.
For
neutral
molecules,
this
leads
to
a
resonance
structure
in
which
the

electronegative
atom
has
a
negative
charge
and
the
less
electronegative
atom
is
left
positively

charged.



To
draw
alternative
resonance
structures
matching
this
pattern,
follow
these
steps:



1.

 Push
the
pi
bond
electrons
from
the
double
or
triple
bond
onto
the


 electronegative
atom
as
a
lone
pair.


 Start
with
an
arrow
from
the
middle
of
the
double
or
triple
bond
and
point
it
toward


 the
electronegative
atom,
showing
how
the
pi
bond
electrons
are
reassigned
as
a


 lone
pair
onto
the
more
electronegative
atom.



2.

 Draw
the
resonance
structure
and
check
the
charges.


 The
electronegative
atom,
having
accepted
electrons
as
a
lone
pair,
should’ve

become


 one
charge
more
negative
in
the
resonance
structure
than
it
began.
Thus,
if

 the


g

 electronegative
atom
started
positive,
it
should
become
neutral
in
the
resonance


or

 structure.
Likewise,
the
more
electropositive
atom
should’ve
become
one
charge


 u.
unit
more
positive
in
the
resonance
structure
than
it
began.

s4
***

 A
lone
pair
or
empty
orbital
cannot
interact
with
a
π
bond
to
which
it
is
orthogonal


 (perpendicular).
E.g.

va
an


 
 

.c



w

Q.
Draw
the
other
resonance
structure
for
the
following
molecules
by
arrow‐pushing.

w



w


 
 
 
 


 (a)
 
 




(b)
 
 






(c)

 
 (d)
 
 





(e)



Answers:













 















Drawing
Multiple
Resonance
Structures


g
or


Sometimes
a
compound
has
a
number
of
resonance
structures.
Practicing
on
a
few
of
these

u.
molecules
that
need
to
be
described
with
multiple
resonance
structures
is
a
good
idea
so
you

s4
can
get
some
more
practice
at
spotting
molecules
that
have
resonance
structures.

To
draw
multiple
resonance
structures,
follow
these
steps:

va



an

1.

 Look
for
one
of
the
patterns
to
find
a
first
alternative
resonance
structure.


 The
four
patterns
are
as
follows:

.c



w

• Cations
next
to
a
double
bond,
triple
bond,
or
lone
pair

w

• Lone
pairs
next
to
a
double
or
triple
bond

w

• Double
or
triple
bonds
containing
an
electronegative
atom

• Double
bonds
alternating
around
a
ring



2.

 After
drawing
the
alternative
resonance
structure,
look
for
additional
patterns


 in
the
new
resonance
structure.


 Often,
drawing
a
resonance
structure
leads
to
a
structure
that
meets
one
of
the


 preceding
patterns,
in
which
case
an
additional
resonance
structure
can
be
drawn.


 Repeat
this
step
until
you
can’t
find
any
more
alternative
resonance
structures.







Q.
Draw
all
the
resonance
structures
for
the
following
molecules
by
arrow‐pushing.





 
 
 


 (a)
 
 




(b)
 
 
 (c)





 
 


 (d)
 
 
 
 
 (e)



Answers:




g
or


u. 

s4
va
an





.c
w
w



w
















 Assigning
Importance
to
Resonance
Structures



A
molecule
with
more
than
one
resonance
structure
looks
like
the
hybrid
of
all
the
resonance

structures
—
but
not
all
resonance
structures
necessarily
contribute
equally
to
the
overall

hybrid.
In
other
words,
if
a
molecule
has
two
resonance
structures,
the
actual
structure
may

look
more
like
one
resonance
structure
than
the
other.

Generally,
resonance
structures
that
correspond
to
stable
structures
contribute
more
to
the

overall
hybrid
than
do
resonance
structures
that
are
less
stable.
So
how
do
you
determine

stability?
Here
are
some
general
guidelines:



• Resonance
structures
with
fewer
charges
are
more
stable
than
resonance

structures
with
more
charges.
For
example,
a
resonance
structure
that
has
no


g
charges
contributes
more
to
the
overall
hybrid
than
a
resonance
structure
that
has


or
two.
This
rule
comes
as
a
result
of
the
energy
cost
of
separating
charges.

• 
 u.
s4
va


 



an

• For
those
molecules
that
are
charged,
the
most
stable
resonance
structures
are

.c

the
ones
that
place
the
charge
on
the
best
atom.
Negative
charges
prefer
to
rest
on

w

electronegative
atoms
(like
oxygen
and
nitrogen),
and
positive
charges
prefer
to
rest

on
electropositive
atoms
(like
carbon).

w



w


 



• Resonance
structures
that
have
all
atoms
with
complete
octets
of
electrons
are

more
stable
than
resonance
structures
that
have
atoms
with
incomplete
octets.

This
rule
comes
as
a
result
of
the
desire
of
atoms
to
own
a
complete
octet
of
electrons.




 

• The
desire
of
a
molecule
to
have
all
atoms
with
complete
octets
trumps
the

desire
to
put
the
charge
on
the
best
atoms.




Q.
Predict
which
resonance
structure
of
the
following
molecule
contributes
more
to
the

overall
hybrid.




g


Answer:


or



u.
s4
va
an





.c

In
this
example,
the
right‐hand
resonance
structure
is
more
stable
than
the
one
on
the
left.
In

w

the
right
resonance
structure,
all
atoms
own
complete
octets
of
electrons,
whereas
in
the
left

w

structure,
the
carbon
is
two
electrons
short
of
an
octet.

w

Thus,
even
though
a
positive
charge
prefers
to
rest
on
carbon
rather
than
oxygen
(because

carbon
is
more
electropositive
than
oxygen),
the
desire
of
a
molecule
to
have
filled
octets

trumps
the
desire
to
put
the
charge
on
the
best
atoms.
Therefore,
the
actual
structure
is
a

mixture
of
the
two
resonance
structures
but
looks
more
like
the
resonance
structure
on
the

right
than
the
one
on
the
left.



Q.
Predict
which
resonance
structure
of
the
following
molecules
contributes
more
to
the

overall
hybrid.























Answers:




g
or
u.
s4


va

The
neutral
resonance
structure
contributes
more
to
the
overall
hybrid
(the
actual
structure)

because
separating
charges
costs
energy.

an



.c
w
w
w





The
left‐hand
resonance
structure
in
which
the
negative
charge
rests
on
oxygen
contributes

more
to
the
overall
hybrid.








The
resonance
structure
that
contributes
most
to
the
overall
hybrid
is
the
right‐most

structure
because
this
structure
has
all
atoms
with
complete
octets
of
electrons.
Recall
that

the
desire
to
have
all
atoms
with
complete
octets
trumps
the
desire
to
put
the
charges
onto

the
most
desirable
atoms.










Trick
question!
Both
resonance
structures
are
equally
stable,
so
both
contribute
equally
to
the

overall
hybrid.




g



or
Q.
Do
you
think
delocalization
as
shown
by
the
following
resonance
structures
is
important?

Explain
why
or
why
not.


 u.
s4
va



an



Answer:



.c

The
resonance
forms
with
a
positive
charge
on
nitrogen
or
oxygen
do
not
contribute

w

significantly
to
stabilization
of
the
positive
charge,
because
the
nitrogen
and
oxygen
do
not

w

have
an
octet
of
electrons
when
they
bear
the
positive
charge.
The
fact
that
oxygen
or

w

nitrogen
does
not
have
an
octet
is
a
critical
point.
When
oxygen
and
nitrogen
do
have
an
octet,

they
can
contribute
significantly
to
a
resonance
hybrid
in
which
they
are
positively
charged.

For
example,
the
adjacent
oxygen
stabilizes
the
1‐methoxyethyl
carbocation
significantly: