Chapter 1: Reaction mechanisms

Learning Objectives
By the end of this section, you should be able to apply concepts related to basic organic techniques
such as:

• Identify the four main types of reactions.

• Differentiate homolytic and heterolytic fissions.
• Compare and contrast reaction mechanisms and equations.
• Define free radicals, electrophiles and nucleophiles.
• Define ‘Lewis acid’ and ‘Lewis base’ and relate them to electrophiles and nucleophiles.
• Describe the formation of intermediates such as free radicals, carbocations and carbanions.
• Illustrate simple mechanisms involving nucleophiles, electrophiles, intermediates and transition
states.
• Apply concepts related to basic organic techniques such Thin-Layer Chromatography (TLC), reflux,
distillation, recrystallisation, filtration and extraction.
• Draw mechanism using Chemdraw software.
Recap types of reaction:

1. Addition reactions
 Unsaturated starting materials (Double bonds)
 2 reactants  1 product
E.g.

2. Elimination reactions
 Saturated starting materials (Single bonds)
 1 reactant  2 products
E.g.

3. Substitution reactions
 2 reactants exchange atoms  2 products
E.g.

4. Rearrangement reactions
 1 reactant reorganise bonds and atoms  1 isomeric product
E.g.
Types of bond breaking

 Carbon intermediates often arise from 2 types of bond cleavage:

1. Homolytic fission (Non-polar breaking):

 From 2 bonding electrons  1 atom receives 1 electron each

 More common than Heterolytic fission
 Involves a non-polar bond
 It forms free radicals
 They have no overall charge because protons = electrons
 They are highly reactive as the unpaired electron has a strong tendency to
pair up with another electron from another atom
 Carbon radical: A carbon atom with 1 unpaired e-

2. Heterolytic fission (polar bond breaking):

 From 2 bonding electrons  1 atom receives both 2 shared electrons

 Involves a polar bond (E.g. )

 It forms ions
 The atom which gains the 2 electrons  ( - )anions
 The atom which loses the 2 electrons  (+) cations
 A (+) carbon ion is a carbocation: It has 6 e- and 3 bonds. They are electron
deficient species and are considered electrophiles.
 A (-) carbon ion is a carboanion: It has an unshared pair of e- and 3 bonds.
They are electron rich species and are considered nucleophiles.

 Carbon Radicals, Carbocations and carbanions are highly reactive species , and are short
lived in an organic mechanism.
Reaction mechanisms

 A balanced chemical equation shows only the overall change which occurs in a reaction
 Understanding how a reaction works through its mechanism is important as it allows us
to predict the products of similar reactions without having to memorise the reagents
and products of a series of related reactions.
 A reaction mechanism shows how a reaction occurs:
 Intermediate steps (which bonds are broken or formed in what order)
 Intermediates
 The relative rate of reaction of each step

Elementary steps
 A step within the organic mechanism
 For reactions with only one step it is known as an elementary reaction.

Rate determining step (Slow step)

E.g.
Step 1: 2A + B  C (Slow, rate determining)
Step 2: C + B  D (Fast)

 Elementary steps in a mechanism do not have the same rate. Usually one of the steps is
much slower and limits how fast the overall reaction proceeds. This is the rate
determining step.

Intermediates
E.g.
A+BX
X+CD
A + B + C D Overall reaction

 X in this example is an intermediate

 Organic reactions usually take place in more than 1 step and involves the formation of a
reactant intermediate which exist momentarily.
 An intermediate results from either homolysis or heterolysis of a bond.
 Usually are free radicals, cations or anions which are highly reactive and unstable.
Chemical kinetics

 Collision Theory: States that not all collisions in a reaction lead to a successful reaction.
Colliding molecules need to collide with the right activation energy (Ea) and right orientation in
order to have an effective collision.
 Activation energy (Ea) : The minimum energy of reactants before a reaction can occur.

Rate Law (reactants)= k[A]x[B]y

 Order of reaction (x, y) : defines how much the rate is affected by the concentration of a
reactant.
 Rate: [reactant]0  the rate does not change, regardless of conc of reactant
 Rate: [reactant]1  when conc doubles, rates doubles (proportional)
 Rate: [reactant]2  the conc doubles, rate increases by 22 (4 times)

 3 ways to determine the rate of reaction:

1) Graphical

2) Calculation from experimental data

E.g. rate = k[F2]1 [ClO2]y

Experiment [F ](M) [ClO ](M) Initial Rate (M/s)

2 2

1 0.10 0.010 –3
1.2 x 10

2 0.10 0.040 –3
4.8 x 10
rate2
=k ¿ ¿
rate1
4 ¿ 4 y  y = 1  rate = k[F2][ClO2]

3) Organic Mechanism

 The stoichiometric coefficient of a given reactant in the rate determining elementary step
("slow" step), is the order of reaction of that reactant in the OVERALL rate equation.

E.g.
Step 1: 2A + B  C (Slow, rate determining)
Step 2: C + B  D (Fast)

Rate law: K [A]2 [B]

Transition states

 Transition state theory: Suggests that there is a species existing at the point where reactants are
just about to be transformed into products.
 This species is termed transition state OR activated complex
 It is extremely unstable, with partial bonds.
 It can decompose either into reactants or products

E.g.
A+BX
X+CD
A + B + C D Overall reaction

 In this example, there is 1 intermediate step (valley) and 2 transition states (Arrows in eq / peak)

Energy profile diagram

 Useful in understanding the transition state in a reaction process and shows how the energy of
reacting particles changes as the reaction progresses.
Reactants

Electrophiles and nucleophiles

 They react by their attraction to each other

 Electrophiles (‘electron lovers’) are short of electrons and accept electron pairs, can be
neutral or + charged

 Nucleophile (‘Nucleus lovers’) are electron rich and donate electron pairs, can be neutral
or – charged

Nucleophiles Electrophiles
- Negative charge - Positively charged (cations)
- Carbanions - Carbocations
- Cl-, Br-, I-, OH- - Exceptions: NH4+/ H3O+ as full octet
 cannot receive electrons
- Bases - Acids
- X – OH (X: Grp 1) - H-X (X: Halogens)
- Y – (OH)2 (Y: Grp 2) - HNO3, H2SO4, HClO3, HClO4
- Amines (are basic)

- Species with lone pairs of e- with polar bonds: - Species with vacant orbitals
H2O, R-OH, NH3, R-NH2, RS - Grp 13 halides E.g., AlBr3

- Exceptions: H2O + NH3, in this case NH3 (base)

will act as the nucleophile
- Carbon-carbon Pi bonds - More electropositive species in polar
- C=C, C ≡ C, C≡N bonds; resulting in great
- AKA alkene or alkynes electronegativity difference
- Alkyl halides (R-X) E.g., CH3Br
- C-X (X: Br, Cl, I)
- Carbonyl C=O
Drawing mechanisms

Guidelines:
 A full arrow ( ) indicates the movement of a pair of electrons and a half arrow ( )
indicates the movement of an unpaired electron.
 Electrons always move from an electron rich(-) source to an electron poor(+) sink.
 Arrows indicate the movement of electrons, not atoms. Do not draw from the 'atom'.
 Deprotonation is required for a neutral nucleophile after substitution

- STEPs are on the next page-

 Steps:

Step 1
Draw skeletal structures of the reactants, include lone pairs on N/O/S and ∂+ / ∂- on polar bonds

Step 2
Identify any acids (such as hydronium ion) or bases where the acid will lose a hydrogen
(deprotonate) and a base will gain a hydrogen (protonate)
E.g. (not in current example)

Step 3
Identify the nucleophilic site (Available electrons on an atom partial negative charge, greatest partial
negative charge) and electrophilic site (partial positive charge, greatest partial positive charge) In
ions: look at the atom with the additional/missing e - to decide.

Step 4
Draw a curly arrow from the nucleophilic site to the electrophilic site forming a bond between the 2
sites.
Note: in acid and base reactions there is an indirect transfer of e -

Step 5
A charged nucleophilic site will be uncharged in the product
An uncharged nucleophilic site will have a positive charge in the product

Step 6
If a new bond is made to a neutral atom, then a second curly arrow is drawn to show cleavage of a
second (polar) bond – the most electronegative atom accepts the e -

Step 7
Add any charges – the overall charge of the reactants is the same as the products.