INORGANIC CHEMISTRY

CONCEPTS

Introduction to Bioinorganic Chemistry

Esperanza Galarza
2019
CONCEPT OF HARDNESS AND SOFTNESS OF ACIDS AND BASES
In 1963 Pearson introduced the concept of hard and soft acids and bases from
observations about the stability of certain metal complexes.

 Hard acids are those cations of small size and high load, of low polarizability:
alkaline, light alkaline earth, high load transition cations, such as Ti4+, Cr3+, Fe3+, Co2+,
etc.

 Soft acids are chemical species of large size, small or no charge, of greater
polarizability: heavier metals and lower load, such as Ag+, Cu+, Pt2+, Hg2+, etc.

 Hard bases are poorly polarizable anions, difficult to oxidize: N >> P> As> Sb; Or
>> S> Se> Te; F> Cl> Br> I.

 Soft bases have high polarizability, low electronegativity, are easily oxidizable and
have unoccupied internal orbitals: N <<P> As> Sb; O << S <Se ~ Te; F <Cl <Br <I.

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 CLASSIFICATION OF CHEMICAL SPECIES
ACCORDING TO THEIR HARDNESS OR SOFTNESS

Hard acids Soft acids

Ions of alkali metals

Heavy element transition metals
Ions of alkaline earth metals

Transition metals with high oxidation Transition metal ions with low
states oxidation states
Hydronium (H+)

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 CLASSIFICATION OF CHEMICAL SPECIES
ACCORDING TO THEIR HARDNESS OR SOFTNESS

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 ACIDS AND BASES: HARDNESS OR SOFTNESS
Pearson (1963):
Species that appear predilection for one group (hard or soft) over the other are
referred to as the preference group.
Hard acids prefer ligands or hard bases, and soft acids prefer soft bases.
The stability of the complex increases when its components match in hardness
or softness.
Ex: AsB + Ah  As + AhB

Therefore B is a hard base

The subscripts h and s denote hardness or softness.

In this way a complete classification of hardness or softness of species was

made.
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 ACIDS AND BASES: HARDNESS OR SOFTNESS
Analysis of the hardness and softness phenomenon

Several forces influence a species to be soft or hard:

 The polarizability of a species determines to a greater extent its hardness

or softness.
Less polarizability  greater hardness
Greater polarizability  greater softness
Factors such as size and electronegative species have a direct influence on
polarizability.

 Electronegativity: Compounds formed by hard pairs form ionic, highly polar

bonds:

Ions of highly electropositive atoms with ions of highly electronegative atoms.

 Size: The smaller the ions involved, the greater the attraction.

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 VALENCE BOND THEORY
According to this theory a covalent bond is formed between two atoms by the
overlap of half filled valence atomic orbitals of each atom containing one
unpaired electron.

More probable to
find electrons in the bond
region
 MOLECULAR ORBITAL (MO) THEORY
MO describes the electronic structure of molecules using quantum mechanics.
Electrons are not assigned to individual bonds between atoms, but are treated as
moving under the influence of the nuclei in the whole molecule.

Linear combination of atomic

orbitals
 COMPLEXES
Coordination complex: central atom or ion, which is usually metallic and is
called the coordination centre, and a surrounding array of bound molecules or
ions, known as ligands or complexing agents.

METAL
LIGANDS L:⟶M

Cisplatin
 ATOMIC ORBITALS INVOLVED IN THE METAL-LIGAND
INTERACTION

s orbitals, l=0 d orbitals, l=2

p orbitals, l=1 d orbitals, l=2

M L M
ATOMIC ORBITALS INVOLVED IN THE METAL-LIGAND
INTERACTION

F orbitals, l=3
 ESSENTIAL TRANSITION METALS FOR HUMANS

Essential Transition metals for humans, are present at considerably lower concentrations than
the elements of the main group such as sodium, potassium, calcium, etc., and contribute little
to isotonic pressure via their solvation properties.

 The elements in their metabolic state are found as Mn+ cations

 The presence of ligands (biological medium) reacts producing
the complexes:

Mn+ + nL MLn
 COMPLEXES STABILITY

 Metal cations form more stable compounds with multidentate ligands than monodentate.

 Formation constants give information about the stability of the complex.

A bidentate ligand produces

more stable complexes
Log K1 = 10.6 Hº = -54 Kj/mol Sº = + 23 J/K mol

Log 2 = 7.7 Hº = -46 Kj/mol Sº = -8.4 J/K mol

En: Ethylenediamine