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Arrow pushing

physical science Maturity 9-11 Next article →

Arrow pushing, also known as electron pushing, is a vital technique in chemistry. It is used to describe the progression of organic reaction mechanisms. A reaction mechanism is the step-by-step path a chemical change follows. By using this method, chemists can visualize how molecules transform during a reaction.

Structuresandmolecules
Structuresandmolecules

While it is a very useful tool, it is important to remember that arrow pushing is a formalism. In reality, electrons or electron density do not move as neatly or discretely as the drawings suggest. However, the technique remains essential for understanding how atoms rearrange themselves.

To use this technique, chemists draw curved arrows on the structural formulae of reactants. These arrows illustrate the movement of electron density. It is a common mistake to think these arrows show the movement of atoms. Instead, they show how electrons move, which indirectly shows how atoms move.

Curved arrow electron pair
Curved arrow electron pair

The tail of an arrow is drawn at an electron source. This could be a lone pair of electrons or a chemical bond. The head of the arrow points toward an electron sink. An electron sink is an area with relatively low electron density that can accept electrons.

Curved arrow single electron
Curved arrow single electron

There are two main types of arrows used in organic chemistry. A single-barbed arrow, often called a "fish hook," represents the trajectory of a single electron. A double-barbed arrow is used to show the movement of an electron pair.

Curved arrow single electron
Curved arrow single electron

When a chemical bond breaks, the electrons leave their original position. The arrow points away from the bond and toward a new location. This could be a specific atom or a new bond. For example, electrons can move to a single sigma bond to create a double pi bond. Because electrons always move to a new atom when pushed, the arrow must always point toward a specific destination.

Chemists recognize two distinct ways that a covalent bond can break. The first process is called homolytic cleavage. In homolytic cleavage, the electron pair that makes up the bond is split.

Homolytic bond cleavage
Homolytic bond cleavage

This is shown using two single-barbed fish hook arrows pointing away from the bond. Each atom retains one single, unpaired electron. These species are known as free radicals. This process often requires energy from heat or light to occur. For instance, ultraviolet light can cause a chlorine-chlorine bond to break homolytically.

Homolytic bond cleavage Cl2
Homolytic bond cleavage Cl2

The second process is called heterolytic cleavage. In this process, the entire electron pair moves to just one of the atoms.

Heterolytic bond cleavage
Heterolytic bond cleavage

This causes the bond to break and creates two different types of ions. One species becomes a negatively charged anion because it kept the electrons. The other species becomes a positively charged cation because it lost them. The anion usually forms on the most electronegative atom. This is because electronegative atoms naturally attract electrons more strongly.

Arrow pushing is used to explain many different types of chemical reactions. In acid-base reactions, a base donates a lone pair of electrons to an acid. In SN1 reactions, a molecule first separates into positive and negative components through solvolysis.

SN1 reaction arrow-pushing
SN1 reaction arrow-pushing

The rate of an SN1 reaction depends only on the concentration of the haloalkane. In contrast, an SN2 reaction is a concerted process where bonds break and form at the same time.

Sn2-arrows
Sn2-arrows

This displacement happens in one step and is called a bimolecular process. There are also elimination reactions, such as E1 and E2, which can compete with substitution reactions.

This scientific method has a long history of development. Sir Robert Robinson first developed the use of curved arrows in 1922. Since his discovery, the technique has expanded significantly. While it began in organic chemistry, it has been extended to inorganic chemistry as well. It is now used to study s- and p-block elements. It has also proven to be effective for describing the chemistry of hypervalent compounds.

E2-mechanism
E2-mechanism

Today, arrow pushing helps scientists across many fields understand the complex logic of molecular interactions.

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🖼️ Images & Media (15)
File:Structuresandmolecules.svg
Structuresandmolecules.svg
File:Curved_arrow_electron_pair.svg
Curved_arrow_electron_pair.svg
File:Curved_arrow_single_electron.svg
Curved_arrow_single_electron.svg
File:Homolytic bond cleavage.svg
Homolytic bond cleavage.svg
File:Homolytic bond cleavage Cl2.svg
Homolytic bond cleavage Cl2.svg
File:Heterolytic bond cleavage.svg
Heterolytic bond cleavage.svg
File:SN1 reaction arrow-pushing.svg
SN1 reaction arrow-pushing.svg
File:Sn2-arrows.png
Sn2-arrows.png
File:E1-mechanism.svg
E1-mechanism.svg
File:E1part2.png
E1part2.png
File:E2-mechanism.svg
E2-mechanism.svg
File:Mechanismus der Sn2 Reaktion.svg
Mechanismus der Sn2 Reaktion.svg

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