Introduction to Reaction mechanisms

Definition
• A reaction mechanism is the step by step
sequence of elementary reactions by which
overall chemical change occurs.
• It is also a detailed description of the process
leading from the reactants to the products of a
reaction, including a characterization as complete
as possible of the composition, structure, energy
and other properties of reaction intermediates,
products, and transition states.

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 Definitions…
• A unimolecular reaction is a reaction where
there is a single reactant molecular entity that
is involved in the microscopic chemical event
constituting an elementary reaction.
• A bimolecular reaction is where there are two
reactant molecular entities that is involved in
the microscopic chemical event constituting
an elementary reaction.

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 Definitions…
• A Reaction Intermediate is often also defined
as "A molecule that is created and destroyed
during a particular reaction pathway”.
• A stepwise reaction is a chemical reaction with
at least one reaction intermediate and
involving at least two consecutive elementary
reactions.

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 Definitions: homolysis
• A homolysis (or homolytic bond cleavage) is
the cleavage (or fission or dissociation) of a
bond so that each of the molecular fragments
between which the bond is broken retains one
of the bonding electrons.

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• The consequence of this process is the retention of a
single unpaired electron on each of the atoms that
were formerly joined by a bond. These single
electron species are known as free radicals.
• The free radicals are denoted by putting dot over the
symbol of atom or group of atoms.

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 Definitions: heterolysis
• Heterolysis (or Heterolytic bond cleavage) is a
process where the electron pair that
comprised a bond moves to one of the atoms
that was formerly joined by a bond.

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 Definitions: heterolysis
• The bond breaks, forming a negatively
charged species (an anion) and a positively
charged species (a cation).
• The anion is the species that retains the
electrons from the bond while the cation is
stripped of the electrons from the bond.

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 Definitions: heterolytic fission
• Heterolytic fission is unsymmetrical wherein
one of the fragments takes both the electrons
of the shared pair, leaving none on the other.
This results into two charged particles as:

A B

A B

A B
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 Definitions…
• A substitution reaction is a reaction, elementary
or stepwise, in which one atom or group in a
molecular entity is replaced by another atom or
group.
• It is a reaction in which one atom or group in a
molecular entity is replaced by another atom or
group contained in an "attacking" nucleophile
(which is a molecular entity that brings a pair of
electrons) attacks an electrophile.

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 Definitions: Nucleophile
• A nucleophile (nucleus loving species, i.e.
negtively charged): this is a species which is
rich in electrons, and serves as an electron
source.
• In general nucleophiles have lone pairs of
electrons, can have a negative charge, or the
source of electrons is the pie bond.

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 Definitions: Electrophile
• Electrophile (electron loving species i.e.
positively charged): this is a species which is
electron deficient and serves as an electron
sink.
• In general, electrophiles have a vacant orbital
which can accept electrons, or have a
polarised bond which can give off a leaving
group.

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 Definitions: Curly Arrow
• Curly arrow (as the name implies) an arrow
showing migration of electrons from a
nucleophile (an electron-rich species, often
negatively-charged) to an electrophile (an
electron-deficient species, often positively-
charged).

Nu E Nu E
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 More on Curly Arrow
• Note: When a bond is broken, electrons leave
where the bond was and this is represented
by a curved arrow pointing away from the
bond (nucleophile ) and ending the arrow
pointing towards the electrophilic species

Nu E Nu E

wrong direction

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 Definitions: Acid and Base
• Base: This is a proton acceptor. It is normally
negatively charged, but it can be neutral. A base
can also be a nucleophile under certain
circumstances. The main work of a base is to pull
a proton from a bond. The most common base is
a hydroxide ion, OH-
B- + H-A  B-H + A-
• Acid: This is a proton donor. In general, an acid
can be represented as:
A-H  A- + H+
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 Flow of electrons
• The flow of electrons originates from the
nucleophile to the electrophile e.g.

Nu + E Nu E

• Better still, the use of curly arrow

Nu E Nu E

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Examples of selected mechanisms
R2 R3 R2
Nu R3
C C
R1 + L
L Nu R1

•In this case, the reaction is known as a nucleophilic

substitution.
•The negatively charged nucleophile (Nu) displaces
leaving group (L) which becomes the new
nucleophile.

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B
H R3 R4 R1 R3
C C B H + C C
+ L
R1 R2 L R2 R4

• This is an example of elimination reaction

• The base abstracts the proton, H.
• As a result, the electrons between the C-H bond
go to C-C bond; it becomes a double bond.
• This causes the C-L bond to break to maintain the
octet rule.

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Example of free radical mechanism
R3 R1
R1 R3
RO C C RO C C Step 1
R2 R4 R4
R2
• In step 1, a radical reacts with an alkene to
form a new radical
R1
R3 R1 R3
RO C C OR
RO C C OR Step 2
R4
R2
R2 R4

• In step 2, two radicals reacts together to form

a neutral molecule

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