Inorganic Chemistry HSAB Principle

Hard Acid Soft Base Theory

Introduction

Hard Acid Soft Base Theory is a qualitative concept which was proposed by Ralph Pearson.The
hard-soft acid-base (HSAB) principle is a theory in chemistry that helps to predict the reactivity
of acids and bases. It explains the stability of compounds (metal complexes). mechanisms and
pathways of their chemical reactions.

The theory states that acids and bases can be classified as either hard or soft, and that they
prefer to react with other acids and bases of the same type. 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 (an ion or molecule that donates a pair of
electrons to a central metal atom to form a coordination complex) are electron pair donors, and
thus are Lewis bases. When we discuss hard or soft "bases", we are discussing ligands. For
example Water (H2O), Ammonia (NH3), Carbon monoxide (CO), Chloride (Cl-),Hydroxide
(OH-). 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. HSAB theory is a useful tool to predict thermodynamic stability or kinetic lability
of Metal-Ligand complexes.

Hard-Soft Interaction Principle (HSIP)

According to HSAB concept, hard acids prefer binding to the hard bases to give ionic
complexes, whereas the soft acids prefer binding to soft bases to give covalent complexes. It is
sometimes referred to as Hard-Soft Interaction Principle (HSIP)

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Inorganic Chemistry HSAB Principle

The HSAB principle can be used to explain a wide range of chemical phenomena, including
the following:

 The formation of coordination complexes: Hard acids prefer to form complexes with
hard bases, while soft acids prefer to form complexes with soft bases.
 The rates of chemical reactions: Hard acids and bases react more quickly with each
other than soft acids and bases.
 The stability of compounds: Hard acids and bases form more stable compounds than
soft acids and bases.

Hard Acids/Bases:

In general, "Hard" acids and bases have a high charge density, are not very polarizable, and
form bonding interactions that are more ionic in nature. These atoms and ions tend to have
high charge and/or small radius.

Typical Hard Acids: metal ions with high positive charges and smaller ionic sizes tend to be
hard acids. Early transition metal ions in the 3d series tend to be hard Lewis acids.

Typical Hard Bases: Small anions and neutral molecules; heteroatoms of the second row of
the periodic table are typically hard (N,O,F). Some examples of hard acids and bases include:
H+, O2-, OH-, F-, Fe3+, and Al3+. Oxygen atoms are always hard, and N atoms are usually hard.

Oxygen and fluorine are considered hard bases because they are small, have high
electronegativity, and are weakly polarizable.

Small size: Hard bases have small atomic radii, which means that their nuclei are relatively
close to their lone pairs of electrons. This makes the lone pairs of electrons more tightly held
and less available for bonding.

High electronegativity: Hard bases have high electronegativities, which means that they
attract electrons more strongly than other atoms. This makes it more difficult for them to donate
electrons to other atoms.

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Inorganic Chemistry HSAB Principle

Weakly polarizable: Hard bases are weakly polarizable, which means that their electron
clouds are not easily distorted. This makes it more difficult for them to form bonds with other
atoms that have different charges.

The combination of these factors makes oxygen and fluorine hard bases. They are more likely
to form bonds with hard acids, which are also small, have high electronegativity, and are
weakly polarizable.

Soft Acids/Bases:

In general, "Soft" acids or bases have a low charge density, are more polarizable, and form
bonds that are more covalent in nature. These atoms/ions tend to have low charge and/or large
radius.

Typical Soft Acids: Transition metals with (+1) charge (such as Cu+) or that are in the late 4d
and 5d series (like Cd2+ and Hg2+), are classified as soft. Soft acids often include transition
metals in the second and third row of the periodic table that have a +1 or +2 charge, as well as
late transition metals (especially those in the 4d and 5d series) with filled or almost completely
filled d orbitals.

Typical Soft Bases: Larger anions and neutral molecules. For example, I- and S2- are soft bases.

Hard-soft trends for acids

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Inorganic Chemistry HSAB Principle

Hard-soft trends for bases