CURLY ARROWS

Reactions proceed via the movement of electrons from one species to another resulting in the breaking
and forming of bonds. The order in which the bonds are broken and formed is termed the reaction
mechanism and the movement of electrons is shown by curly arrows.
The curly arrow is used to show the movement of the electrons, and therefore must always begin at an
area of high electron density, i.e. a lone pair, a negative charge, a - atom on a molecule, or from the
centre of a single or double bond.
The arrow will then end in a region of low electron density, i.e. a positive charge or + atom in a molecule.
Double-headed arrows are use to show the movement of a pair of electrons, whereas single-headed
arrows show the movement of a single electron. All the arrows that are required to be drawn at A-level
are double-headed arrows.

Double-headed:

Single-headed:
An example of a reaction mechanism shown using curly arrows, would be the reaction between ethene
and hydrogen bromide, an electrophilic substitution mechanism:
1. Firstly the -bond between the two carbon atoms in ethene breaks:

H2C = CH2

H Br

The bond is simply a pair of electrons and these move to form a new bond with the + hydrogen
in HBr.
In this step the curly arrow starts in the centre of the double bond an area of high electron
density, and moves to the + H of the H-Br bond.

2. At the same time, the pair of electrons in the HBr bond move down to the bromine atom and form
the bromide ion, Br-.

H Br

Br- +

CH3 C+H2

Here the curly arrow starts form the electrons in the centre of the H-Br covalent bond and move
to the Br atom forming a bromide ion.
All electron pair movements must be shown as curly arrows and not straight ones.

3. The next stage of this reaction shows how to use a curly arrow if a lone pair of electrons is
involved.
The first step of the electrophilic addition mechanism leaves a positive charge on one of the
carbon atoms of the alkene group, and a negative bromide ion. The electrons shown on the
bromide ion can be thought of as those that originally made up the hydrogen-bromide bond.
There are 3 other lone pairs of electrons around the outside of the bromide ion, however these
are not normally shown because they are not involved in the reaction mechanism. The lone pair
that are involved in the mechanism MUST be shown as a pair of dots on the ion.
The lone pair on the bromide ion moves to form a new bond between the bromine and the
positively charged carbon atom. This movement of electrons is shown as a curly arrow that starts
in the centre of the lone pair on the bromide and ends at the positive carbon.

CH3 C+H2
Br-

This leaves the final product, which in this case is bromoethane:

CH3 CH2Br

The overall reaction mechanism, looks like this:

CH3CH2H

H
H

H
H
Br

CH3CH2
H

CH3CH2

H
+

H
..
Br
primary carbocation

Br

minor product

Common reaction mechanisms are listed below in the table, along with the species which usually react
using them
Mechanism
Electrophilic addition
Nucleophilic substitution
Electrophilic substitution
Nucleophilic addition
Radical substitution

Reaction species
Alkenes
Alcohols and Halogenoalkanes
Arenes
Carbonyls
Alkanes