Lewis concept of acids and bases

Lewis acids and bases are described by the Lewis theory of acid-base reactions as electron-
pair acceptors and electron pair donors respectively. Therefore, a Lewis base can donate a pair of
electrons to a Lewis acid to form a product containing a coordinate covalent bond. This product is
also referred to as a Lewis adduct. An illustration detailing the reaction between a Lewis acid and
base leading to the formation of a coordinate covalent bond between them is given below.

Lewis acids and bases are named after the American chemist Gilbert Newton Lewis, who
also made invaluable contributions in the fields of thermodynamics and photochemistry.
1.1 Lewis Acid
Lewis Acids are the chemical species which have empty orbitals and are able to accept
electron pairs from Lewis bases. This term was classically used to describe chemical species with
a trigonal planar structure and an empty p-orbital. An example of such a Lewis acid would be
BR3 (where R can be a halide or an organic substituent).
Water and some other compounds are considered as both Lewis acids and bases since they can
accept and donate electron pairs based on the reaction.
Examples of Lewis Acids
Some common examples of Lewis acids which can accept electron pairs include:
➢ H+ ions (or protons) can be considered as Lewis acids along with onium ions like H3O+.
➢ The cations of d block elements which display high oxidation states can act as electron pair
acceptors. An example of such a cation is Fe3+.
➢ Cations of metals such as Mg2+ and Li+ can form coordination compounds with water
acting as the ligand. These aquo complexes can accept electron pairs and behave as Lewis
acids.
➢ Carbocations given by H3C+ and other trigonal planar species tend to accept electron pairs.
1.2 Lewis Base
Atomic or molecular chemical species having a highly localized HOMO (The Highest
Occupied Molecular Orbital) act as Lewis bases. These chemical species have the ability to donate
an electron pair to a given Lewis acid in order to form an adduct, as discussed earlier.
The most common Lewis bases are ammonia, alkyl amines, and other conventional amines.
Commonly, Lewis bases are anionic in nature and their base strength generally depends on the
pKa of the corresponding parent acid. Since Lewis bases are electron-rich species that have the
ability to donate electron-pairs, they can be classified as nucleophiles. Similarly, Lewis acids can
be classified as electrophiles (since they behave as electron-pair acceptors).
Examples of Lewis Bases
Examples of Lewis bases which have an ability to donate an electron pair are listed below.
➢ Pyridine and the derivatives of pyridine have the ability to act as electron pair
donors. Thus, these compounds can be classified as Lewis bases.
➢ The compounds in which Oxygen, Sulphur, Selenium, and Tellurium (which belong to
group 16 of the Periodic Table) exhibit an oxidation state of -2 are generally Lewis bases.
Examples of such compounds include water and ketones.
➢ The simple anions which have an electron pair can also act as Lewis bases by donating
these electrons. Examples of such anions include H– and F–. Even some complex anions,
such as the sulfate anion (SO42-) can donate pairs of electrons.
➢ The π-systems which are rich in electrons (such as benzene, ethyne, and ethene) exhibit
great electron pair donating capabilities.
Weak Lewis acids have strong conjugate Lewis bases. Apart from this, many chemical species
having a lone pair of electrons such as CH3– and OH– are identified as Lewis bases due to their
electron pair donating capabilities.

2. Chemical Reactions Between Lewis Acids and Bases

2.1 Reactions with the H+ ion
The H+ ion acts as a Lewis acid and H2O acts as a Lewis base. The reaction between the water
molecule and the proton yields a hydronium ion (H3O+), as illustrated below.
Here, the oxygen atom donates an electron pair to the proton, forming a coordinate covalent
bond in the process. The resulting Lewis acid has a +1 charge associated with it. Another
example of a reaction in which the H+ ion acts as a Lewis acid is its reaction with ammonia
(NH3) to form an ammonium ion (NH4+).

In this reaction, the proton receives an electron pair from the nitrogen atom (belonging to the
ammonia molecule). The formation of a coordinate covalent bond between the two results in the
formation of a Lewis adduct (the ammonium cation).
2.2 Reaction Between Ag+ and Ammonia
In this reaction, two Lewis bases form an adduct with one Lewis acid, as illustrated below.

Here, ammonia acts as a Lewis base and the silver ion acts as a Lewis acid. Each nitrogen atom
donates an electron pair to Ag+, resulting in two separate coordinate covalent bonds. The adduct
formed from the Lewis acid and base has the chemical formula Ag(NH3)2+.
2.3 Reaction Between the Fluoride Ion and Boron Trifluoride
This reaction features the formation of a coordinate bond between the fluoride anion (F-) and
boron trifluoride (BF3).
Here, F– acts as an electron pair donor whereas BF3 accepts the electron pair. The reaction
between the Lewis acid and base results in the formation of an adduct with the chemical formula
BF4–.

3 Applications of Lewis Acids and Bases

Some important applications of Lewis acids and bases are provided below.
1. Lewis acids play a vital role as a catalyst in the Friedel-Crafts reaction – AlCl3 accepts a
lone pair of electrons belonging to the chloride ion leading to the formation of AlCl4– in
the Friedel-Crafts alkylation process.
2. This also leads to the formation of the highly electrophilic carbonium ion which acts as a
strong Lewis Acid. The chemical reaction can be written as follows.
3. RCl + AlCl3 ⟶ R+ + AlCl4–
4. In the field of organic chemistry, Lewis acids are widely used to encourage many cationic
or pseudo-cationic chemical reactions.
5. Lewis bases have immense applications in the modification of the selectivity and the
activity of metallic catalysts. For the production of pharmaceuticals,
asymmetric catalysis is an important part of enantioselective synthesis. In order to enable
asymmetric catalysis, chiral Lewis bases are often used to confer chirality on catalysts.
6. Several Lewis bases have the ability to form many bonds with Lewis acids. These
compounds are also called ‘multidentate Lewis bases’ or ‘chelating agents’ and have a
wide range of industrial and agricultural applications

Hard-Soft Acid and Base (HSAB) concept

Hard and Soft Acid and Base (HSAB) theory allows us to predict which acids and bases
prefer to interact. Recall that Lewis acid-base theory can be applied to describe metal-ligand
interactions. Metal ions are electron pair acceptors, and thus are Lewis Acids. So, when we discuss
hard or soft "acids" in this course, we are discussing metal ions. Ligands are electron pair donors,
and thus are Lewis bases. When we discuss hard or soft "bases", we are discussing ligands.
Softness roughly refers to the polarizability of an acid or base. The larger and more neutral
any species, the softer it is. Conversely, the smaller and more charged a species is, the harder it is.
1.1 Hard and Soft Classification
1.1.1 Hard Species
Hard acids and bases have a high charge density (highly charged relative to size), and
polarization is difficult. Low polarizability is attributed to hard acids being relatively electron-
poor and hard bases being relatively electron-rich. Low polarizability is also attributed to the
localization of charge on an atom with electron-withdrawing substituents (in the case of a hard
acid) or electron-donating substituents (in the case of a hard base). It is also observed that hard
acids have high oxidation states or large positive formal charges, while hard bases have low
oxidation states or negative formal charges.
For hard acids, which possess few valence electrons, polarization involves distorting core
(inner shell) electrons, which are difficult to distort because they are close to the nucleus and
experience a high nuclear charge. Hard acids tend to be found towards the left side of the periodic
table and involve higher oxidation states and/or electron donating substituents
1.1.2 Soft Species
Soft acids and bases possess many valence electrons and are more readily polarized. Soft
acids and bases are more likely to be found towards the middle or right of the periodic table. Soft
acids and bases also have little charge density and/or are relatively electron rich. Soft acids are
more common to the right of the periodic table and involve lower oxidation states and/or electron
donating substituents.
1.1.3 Borderline Species
All hard acids and bases are not equally hard, and all soft acids and bases are not equally
soft. There is a graduation in hardness and softness, and there are a number of intermediate acids
and bases that do not fit neatly in either category. Following Figure classifies each element as a
hard, soft, or borderline (intermediate) acid or base. Some borderline acids can be considered hard
or soft depending on their oxidation state. The higher oxidation state species can be considered
hard acids, and the lower oxidation state species can be considered soft acids. Additional
representative examples of hard, soft, and borderline bases are shown in Figure below.
 HSAB classification of selected species. (CC-BY-NC-SA; Kathryn A. Newton)

1.2 The Hard-Soft Acid-Base Principle (HSAB Principle)

The Hard-Soft Acid-Base Concept (HSAB Concept) explains patterns in Lewis acid-base
reactivity as a like reacts with like preference. Both thermodynamically and kinetically, hard acids
prefer hard bases and soft acids soft bases.
1. Thermodynamically, hard acids form more stable acid-base complexes with hard
bases while soft acids form more stable complexes with soft bases.
2. Kinetically, hard acids/electrophiles react more quickly with hard
bases/nucleophiles while soft acids/electrophiles react more quickly with soft
bases/nucleophiles.
The HSAB principle can predict the equilibrium of Lewis acid-base metathesis and displacement
reactions. In a Lewis acid-base metathesis reaction the acids and bases swap partners: