π Bond Overlap and Resonance

Lets exam π overlap with the conjugated system butadiene, CH2=CHCH=CH2

1.54 Å 1.34 Å 1.50 Å 1.47 Å

H3C CH3 H 2C CH2 H2C CH CH3 H2C CH CH CH2

σ(sp3 - sp3) σ(sp2 - sp2), π(p-p) σ(sp2 - sp3) σ(sp2 - sp2)

1.20 Å 1.46 Å 1.43 Å 1.37 Å

HC CH HC C CH3 HC C CH CH2 HC C C CH
σ,(sp – sp), π(p-p) σ(sp - sp3) σ(sp - sp2) σ(sp – sp)
Why does the bond length between the carbon-carbon single bonds become smaller
as the hybridization changes from sp3 to sp?
Because the sp3 orbitals have more p character and are longer. The more s character the orbital has
the smaller and shorter it is. Sp3(1/4 s, ¾ p) – sp2 (1/3s, 2/3 p) – sp (1/2 s, ½ p)

Conjugation: systems that have a p orbital on an atom adjacent to a double bond

– molecules with delocalized π bonds – are called conjugate unsaturated systems
saturated
unsaturated
conjugated and unsaturated
Sec. 4 - Resonance 1
 What effect does conjugation have of the stability of the molecule?
Hydrogenation
H2/Ni ∆H = -30.3 kcal/mol

We would assume ∆H = 2 x - 30.3 kcal/mol

= - 60.6 kcal/mol
H2/Ni
Observed ∆H = - 57.1 kcal/mol

For an exothermic reaction the more heat given off the less stable the molecule is
Potential Energy

CH2
H2C ∆Hcalc= - 60.6 kJ/mol

∆Hobs= - 57.1 kJ/mol

More stable than
calculated

CH3
H3C

Reaction Coordinate
Sec. 4 - Resonance 2
Conclusion: Two conjugated bonds are not utterly unconnected.
There is some overlap of adjacent π electrons which shortens the C2 –C3
bond and helps stabilize the molecule. Although, this overlap is small
What is causing the overlap of adjacent π electrons
Lets look at resonance structures
H H H H
+
H C 3 C4 H C C
C 2 C H C C H
most stable 1
resonance H H H H
form

H H H H
+
H C C H C C
C C H C C H

H H H H

Best resonance form shows alternating double and single bonds. But some
double bond character is possible between carbons 2 and 3.
Sec. 4 - Resonance 3
 Lets look at the π molecular orbitals to see what influence the
overlap between the 2p orbitals have on carbons 2 and 3

more nodes
less stable

LUMO – Lowest
Unoccupied Molecular
Orbital

HOMO – Highest
Occupied Molecular
Orbital dictates
molecular orbitals
attributes. Shows double
bond character between
C1-C2 and C2-C3
The linear
combination of
4 atomic
orbitals gives Both models predict the shortening of the C2 – C3 bond
4 molecular because of p overlap.
orbitals Also the sp2 orbital has more s character than an sp3 hybrid
orbital. Sec. 4 - Resonance 4
Now lets look at the stability of benzene, a conjugated system that is a ring

Benzene is much more stable than would be expected based on

calculations for “cyclohexatriene”, isolated double bonds. sh
g ort
Theoretical; 3 x -120 =-360 kJ/mol lon
Observed = -208 kJ/mol hypothetical potential
Dif = 152 kJ/mol energy if the double
bonds were isolated

Theoretical; 2 x -120 =-240 kJ/mol cyclohexatriene

Observed = -232 kJ/mol
Dif = 8 kJ/mol

far more stable

than calculated

Benzene
C6H6

Sec. 4 - Resonance 5
Experimentally what is the shape of benzene?

C-C bond length is between: 6 atomic p orbitals Overlap of the p orbitals

1.34 Å 1.47 Å around the results in a
H2C CH CH CH2 molecular orbital
encompassing the top and
bottom faces of the ring
Ξ

π electrons
resonate
around the ring
Electrostatic potential
map of benzene

Sec. 4 - Resonance 6
 Now that you have knowledge about where electrons are located
in molecules lets look again at resonance structures with new insight!
But first a few more comments about curved arrows:
Curved arrows show the flow of electrons density which will become very important when we
look at organic reactions and see how electron flow creates and breaks bonds. They are used
in resonance structures to help us draw the structures. The resonance structures are all
occurring at the same time and the best way to establish electron density is to determine the
molecular orbitals. But this can be a pain, and resonance structures will give us all the
information we need to know.

the tail shows us where the the head shows where the
electrons are coming from head electrons are going
tail
H H H H
+ H
C + C H H H
H C C C C
C H C H C H C
C C
H H
H H H
H H H
+ O
O
O + H H
H H O H
C C C C H C
C H C C
H H H C
C H
H H H H H
H H
H H
arrows not filled in Sec. 4 - Resonance 7
 Draw the resonance structures of the following molecules

+ If these structures give you problems put

the hydrogens on the carbons.
H H H H
H

H +
H What is the hybridization of each carbon atom?

H H H H
Now think about the electrons in the
unhybridized orbitals. These are the
empty p orbital
electrons that flow over the carbon skeleton
H H H that is linked by sigma bonds. You can not
move sigma bonds because the connection
H
between the carbon atoms would be broken.
+ H
+ +
H +

this system is conjugated In an sp3 hybridized carbon atom all electrons are
and will delocalize or involved in σ bonds This isolates the end (terminal)
resonate. double bond from the other double bonds
Sec. 4 - Resonance 8
 Resonance Structures Remember a double headed arrow
show the movement of two electrons.

The arrow starts at the bond between the

H H H
atoms (where the electrons are)
H
+ + H

The arrow ends between the H

two carbon atoms to show
the formation of a new π bond

H H H
+ +
H
H

H H H
+
H
+++
H
++ ++
H
Sec. 4 - Resonance 9
 +
a
sp
2 a b sp 2 N
+ sp3 sp3 sp2
b H
sp2 N +
sp2 sp2 sp2
H N
a b
H
+ H H
+
N
N
H
H b
+ H H
a
+ H H
N

H
N

H
H H

N +
H
Sec. 4 - Resonance 10
 H H
2 H
3
4
H sp3 5 valence electrons,
1 sp2
sp2 should have 4  -ve
sp3 H

H H The arrow starts at the carbon atom

The blue arrow is needed where the lone pair is. A charge can only
because you can not have 10 be on an atom since it is the imbalance
electrons around the carbon between and electrons and protons.
atom. The arrow starts The arrow ends between the two
between the carbon atoms, carbon atoms to show the formation
(the π bond) and ends on the of a new π bond
carbon atom
H CH3

H H

H H CH3
CH3
H H H CH3
H H
H H
3 atomic orbitals will
form 3 molecular orbitals 4
Resonance structures 4 p electrons H CH3
and molecular orbitals
H H
show –ve charge on
Sec. 4 - Resonance 11
carbons 1 and 3
1 2 3
 O O O O

If you have trouble thinking about the formal charge put hydrogens on

The carbon has H H

5 valence electrons,
should have 4  -ve
H H

H3C C O

Sec. 4 - Resonance 12
 Ultra Violet and Visible Spectroscopy
•The visible spectrum spans from about 400 nm (violet) to 750 nm (red)
and the ultraviolet spectrum ranges from 100 to 400 nm

Chart obtained from the web site: http://www.cem.msu.edu/~reusch/VirtualText/Spectrpy/UV-Vis/spectrum.htm

Sec. 4 - Resonance 13
 Ultra Violet and visible Spectroscopy
•Certain molecules will absorb electromagnetic radiation in this region.
•When absorption occurs atoms or molecules pass from a state of low energy
(ground state) to a state of higher energy (excited state).
•Generally the most probable transition is from the HOMO to the LUMO
•Molecules that require more energy for electron promotion absorb at shorter
wavelengths and molecules that require less energy absorb at longer
wavelengths.

π* When the electron

π  π* transition drops back the energy
π is dissipated as heat,
171 nm light or can cause
H2C CH2 chemical reactions
or 686
kJ/mol
Absorption of a photon

Sec. 4 - Resonance 14
 Electronic Energy Level Transitions

σ*

π*
} Unoccupied Levels

n  π* n  σ* π  π* σ  σ*
Energy

}
n

Occupied Levels
π

σ  σ* - Alkanes These transition states are of such high energy that they absorb ultraviolet energy
at very short wavelengths – below 200 nm and are shorter than what can be typically measured - Ethane
λ max = 135 nm. Alkenes are good for solvents since they are transparent in the accessible UV region.
n  σ* - Alcohols, ethers, amines and sulfur compounds Also high energy but are observable in the UV
spectrum – 175 to 200 nm however this is the range were most solvents absorb thus obscuring the peak.
π π* - Alkenes and Alkynes. Also high energy but their position is sensitive to the presence of
substitution – Ethene λ max = 165 nm

n  π* - Carbonyl compounds occur around 280 – 290 nm and are of low intensity.

Sec. 4 - Resonance 15
 Acetone is a molecule that undergoes both
π  π* and n  π* transitions

π*
π*

n
n

π
π π* π  π*
n  π*
excited state excited state
n
279 nm 187 nm
Two lone π
pairs of e-
ground
O
state

H3C CH3
acetone

Sec. 4 - Resonance 16
 What do these Transitions look like?

C C σ ∗ CC

C C

σ  σ∗
C C σ CC
antibonding orbitals
are outlined in dots
H H
H
C C H
H H

C C

σ  σ∗
Sec. 4 - Resonance 17
C N
σ ∗ CN

C N

C N n(sp3)
n  σ*

C N σ CN C N

H
C N
H H
H H Sec. 4 - Resonance 18
C C C C

π ∗ CC

π  π∗

C C π CC

C C

H H
C C
H H
Sec. 4 - Resonance 19
 What are the electronic transitions
for the carbonyl group?
C O
σ ∗ CO

C O
π ∗ CO

C O n  π∗
C O
n(py)

C O
π CO

C O
σ CO

C O C O
π  π∗
n(sp)CO

R
C O
R Sec. 4 - Resonance 20
 Effect of Conjugation
As the conjugation increases generally the deference in energy between the
HOMO and LUMO decreases. The narrowing of the gap between the HOMO
and LUMO gives a lower energy, longer wavelength absorption.

π4* π6*
π2* π5*
π3*
171 nm π4*
217 nm 258 nm
π3
π2
π1
π2
H2C CH2 π1
π1
CH2 CH2
H2C H2C

This is called a bathochromic shift or red shift –

a shift to lower energy or longer wavelength
258
When the reverse effect is experienced it is
called a Hypsochromic shift or (blue shift – a UV Spectra of conjugate alkenes
shift to a higher energy or shorter wavelength. http://www.cem.msu.edu/~reusch/VirtualText/Spect
rpy/UV-Vis/spectrum.htm
Sec. 4 - Resonance 21
 A compound that contains a longer chain of conjugated double
bonds absorbs light at a longer wavelengths
H3C
CH3 CH3 CH3 H3C

CH3 CH3 CH3 CH3

CH3

 β-carotene – 11 conjugated double bonds.

• It is the principle compound responsible for giving carrots their orange
color.
• Carotene derivatives provide many of the colors we see in fruits,
vegetables and autumn leaves.
• It absorbs light at 454 nm, well into the visible region which corresponds to
the absorption of blue light.
• White light in which blue light has been removed appears orange.

Compounds that absorb light in the visible region have more-easily promoted
electrons than compounds that absorb at shorter UV wavelengths.

Absorption at 100 nm (UV) 750 nm (visible)

Increasing ease of electronic transition
Sec. 4 - Resonance 22
 Absorption Spectra
Many of the colors we see are caused by the absorption or subtraction of
specific wavelengths from white light and we observe the reflected light

Wavelength, nm Color Observed or

absorbed reflected color

400 Violet Yellow

450 Blue Orange
500 Blue-green Red
550 Yellow Violet
600 Orange-red Blue-green
700 Red Green

π*

We see red
π
White
light Absorption of a green

Sec. 4 - Resonance 23
 Absorption by Aromatic Systems

UV/visible spectra of aromatic compounds is more complex with many

more peaks because of the many low lying π* orbitals. The absorption
spectra of polycyclic aromatic systems is shifted to longer wavelengths
as the number of rings is increased because of increasing conjugation
and greater resonance stabilization.

Benzene Anthracene
αmax = 260 nm αmax = 375 nm
(yellow)
Pentacene
αmax = 575 nm
(blue)

Naphthalene Tetracene
αmax = 280 nm αmax = 375 nm
(yellow)

λ max = wavelength of maximum absorption.

λ max will change with different solvents
Sec. 4 - Resonance 24
UV Spectra of naphthalene, anthracene, and tetracene: obtained from the
web site, http://www.cem.msu.edu/~reusch/VirtualText/Spectrpy/UV-
Vis/spectrum.htm

Sec. 4 - Resonance 25
 Colored Compounds
Chromophores: certain structures give rise to colors

O
O
π  π*
+
N N N

Auxochromes: Substituents that increase the intensity of absorption and possibly

the wavelength
OH OR NH2 NRH NR2 X n  σ*

Auxochromes can also cause an intensification of color by means of extending

the length of the conjugated system. The nonbonding electrons become part of
the π system of molecular orbitals, increasing its length by one extra orbital. This
has an effect of decreasing the gap between the π  π* transition

+
R B R B

R R R R
Sec. 4 - Resonance 26
 Colored Compounds
CH3
OH O
O HO CH3
HO OH HO
OH
O OH
OH O O
O
HO OH
juglone: partially responsible for
the colour of walnuts
carminic acid: red dye used to dye
food and cosmetics

NH2 H2N
OH O OH HO

OH O 3S SO 3
N N
N N

O SO 3 O 3S

lawsone: henna - red dye Direct Blue 2b: an azo dye used to
dye fabrics

Sec. 4 - Resonance 27
 Sunscreens

Absorption of UV radiation.
UV radiation can cause adjacent thymine bases to form mutagenic dimers.
Sunscreens absorb UV energy by promoting π and nonbonding electrons to
higher energy levels after which the energy is dissipated by relaxation
through molecular vibration. In essence, the UV radiation is converted to
heat. (IR radiation)
UV-A 320: to 400 nm UV-B: 280 to 320 nm UV-C: 100 to 280 nm
UV-C higher energy – most concern – Ozone in the atmosphere absorb UV-C
wavelengths thus we are protected. Tanning and sunburn are caused by UV-
B radiation. Risk of skin cancer is primarily associated with UV-B radiation
although some UV-A wavelengths may be important as well.
O
O OH

OCH2(CH2)6CH3

(H3C)2N Examples
OCH3
Octyl 4-N,N-dimethylaminobenzoate 2-hydroxy-4-methoxybenzophenone
(Padimate O) λ max= 310 (Oxybenzone) λ max= 288 and 325
Sec. 4 - Resonance 28
UV Invisible Inks, Ink Pads and Pens
Fluorescence (emission not
Blacklight / Ultraviolet (UV) Viewable - Isopropyl Alcohol Based absorption)
Our Invisible Ink uses special High-Brightness Ultraviolet (UV) Blacklight Viewable
compounds. The Invisible glows a bright blue and UV or Blacklight including
our special UV flashlight. Under normal light, this ink is completely invisible. This
ink can only be seen when illuminated by a UV or Blacklight emitting in the 350nm
- 385nm light range. The ink is permanent and can be applied to paper, plastic,
skin, wood and almost any substance. The ink does not wash off, but will
eventually wear off if applied to skin.
Depending on the light used, this ink will appear a blue or white depending on UV
light used. Please see pictures below for color appearance
Fluorescence
The energy lost by this
energy lost by internal emission is slightly less than
conversion – heat and the energy absorbed because
molecular motion of internal conversion.
Consequently, the
energy lost as
wavelength of light emitted is
fluorescence
slightly longer than that
absorbed

energy absorbed
Sec. 4 - Resonancehttp://www.maxmax.com/aUVBlueInvisibleInks.htm 29
 Why does white clothing glow under black lights?

To make your clothing appear white optical bleaches are used

as fabric whiteners. These colorless compounds absorb
ultraviolet light just outside the visible range and emits blue-
violet light at the edge of the visible spectrum. This blue-violet
color masks yellowing of the fabric.

SO3- Na+
O O
NH C NH CH CH NH C NH

+
Na -O3S
Blankophor R
CH3

(H3C)2N O O

Calcofluor SD

Sec. 4 - Resonance 30
 What causes blood to glow?
Chemiluminescence (emission not absorption)
Forensic investigators use a compound called Luminol to detect blood.
Luminol is an organic compound that when oxidized emits light with the
evolution of little or no heat. This chemical process is called
chemiluminescence (seen in glow-sticks). In nature it is called
bioluminescence. (fireflies, some jellyfish and fish)
Luminal will glow greenish-blue when it comes in contact with blood
even if it is in trace amounts.

O O * O

- -
NH H2O2/OH O O
H2O + N2 + light
- -
NH catalyst O O
(metal)
NH2 O NH2 O NH2 O

excited

The catalyst can be number of metal ions Cu(II), Co(II) or Fe(III) found
in hemoglobin.
Sec. 4 - Resonance 31