CHM 102: GENERAL CHEMISTRY II
Name of Speaker: Dr. Ebenezer Chukwunonyelu Nnadozie
E x cEexl cl ee nl l ceen, c Se c, hSoc lha or ls ah ri sph ai pn da nPdr oPdr uo cdtiu vc ti
i t vy i t y
Course Highlights:
• Electronic theories in organic Chemistry:
a) Electronegativity
b) Inductive effect
c) Mesomeric (conjugative) effect
d) Electromeric effect
e) Case studies
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Introduction
• Electronic theory can be described as the aspect of
chemistry concerned with the movement of electrons in
organic compound.
• The principles of electronic theories was made popular by
Christopher Kelk Ingold (1893 – 1970), a British chemist.
• Ingold was a physical organic chemist and is credited
with the discovery of concepts such as nucleophile,
electrophile, mesomerism, mesomeric effects etc
• Ingold’s study of alkyl halides led to the discovery of two
possible reaction mechanism for nucleophilic
substitution.
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Introduction
• Electrophile and Nucleophile are
adapted from the root words
electron(-) and nuclueus (+)
• The word phile is adapted from the
Greek word philos which means love
• Therefore electrophile means a
specie rich in positive charge(s) and
are thus electron loving
• Nucleophile implies a specie rich in
negative charge(s) and thus nucleus
loving
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Introduction
• Electronic theories are useful
in describing physical
characteristics, such as dipole
moment and bond length
• The knowledge of electronic
theories helps to describes
the distribution of the charge
in organic compound
• Electronic theories helps to
identify the point of
electrophilic or nucleophilic
attack and thus reaction
mechanism
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Electronegativity
• It is a measure of the attraction of an atom for electrons
• Electronegativity is the induction of a permanent dipole in a
molecule due to the unequal sharing of the bonding
electrons
• The halogen group is the most electronegative group in the
periodic table
• Electronegativity decreases down the group and increases
across the period
• The addition of shell down the group weakens the attractive
force between the positive nucleus and the electron
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Electronegativity
• Consider the bond between
Carbon and chlorine (C – Cl)
• the halogen is more
electronegative than carbon
• Cl would thus attract the shared
electron more strongly to itself
• This would result in the creation of
a permanent dipole
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Inductive effect
• Inductive effect is the
electronic effect induced by
the polarization of bonds in a
molecule or ion.
• It occurs in a chain of carbon
atoms linked by sigma bond.
• It diminishes along the carbon
chain.
• It is almost negligible beyond
the fourth carbon atom.
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Inductive effect
• An inductive effect is
permanent
• The electron drawing atom is
labelled (-I)
• while the electropositive group
is (+I)
• Examples of –I include
hydroxides, halogens, nitro etc
• Examples of +I are methyl,
carboxylate ion
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Mesomeric effect
• This is polarity created between
atoms of a conjugated system
• It occurs when electron(s) is
transferred across a pi bond
• Mesomeric effect occur when π
electrons move away or towards
a substituent group in a
conjugated orbital system
O
O
H2C CH C CH3 H2C CH C CH3
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Mesomeric effect
• +M effect occurs when the
electrons are transferred from a
particular group towards a
CH2 CH CH CH CH CH NH2
conjugate system
• When this occurs the electron
CH2 CH CH CH CH C NH2
density of the conjugated system H
is increased
H
CH2 CH C C CH C NH2
• For +M to occur there should be H H
a lone pair of electron or –vely
charge ions
CH2 CH2 CH CH CH NH2
• Examples of +M groups are –
NR2, -O, -OH, -OR, -F, -Cl
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NH2 NH2 NH2 NH2
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Mesomeric effect
• -M effect occurs when the π bond
electrons are transferred from the O
conjugate system to a particular
group CH2 CH N
O
• When this occurs the electron
density of the conjugated system
is decreased O
CH2 C N
H
• For -M to occur there should be a
vacant orbital or +ve charge ions O
• Examples of -M groups are –NO2, -
CN, -COR, -COOH, -COOR
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Electromeric effect
• Electronic effect is used to
describe the shift of electron
that occurs in an unsaturated
molecule
• Electromeric effect is initiated
by a nucleophile or
electrophile
• The effect is reversible and
involves the complete transfer
of π electrons
• Reversibility occurs when the
external constrain is withdrawn
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Electromeric effect
• In +E effect, the shared electron
pair is transferred towards
the attacking reagent
• The attacking reagent forms a
bond with the atom that has
received the shared pair of
electrons H
H2C CH2 H2C CH3
• The reagent is positively
charged and is seeking a
negatively charged site
• Example is the protonation of
ethene
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Electromeric effect
• In -E effect, the shared electron
pair is transferred away from
the attacking reagent
• The reagent attacks the atom
that has lost its shared pair of H H O
electrons and forms a bond with CN
it C O C
H H CN
• The reagent is negatively
charged (nucleophile) and is
seeking a positively charged
site.
• Example is the nucleophilic
addition of hydrogen cyanide to
the aldehyde and ketone group.
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Case Study 1: Formic acid and acetic acid
Why Formic acid is stronger than acetic acid?
The relative acidity can be explained on the basis of stability of conjugate
bases of the two acids. The following conjugate bases are formed from the
corresponding acids. In acetate ion, the electron releasing methyl group (+I
effect) would intensify the negative charge on COO- ion and thus destabilizes
it. No such effect is present in formate ion (HCOO- ). Hence formate ion is
more stable than acetate ion. Therefore formic acid is stronger acid than
acetic acid
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Case Study 2:mono-, di- and trichloroacetic
acid
It can be said that the presence of
three Cl atoms makes oxygen highly
electron deficient and, thereby,
polarising the O-H bond the most.
Therefore, the acidity order for the
above compounds would be III > II > I.
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