Hard-Soft Acid Base

Theory
Inorganic Chemistry

cidos y bases
Aceptores y donadores

El concepto de Lewis es ms general y puede ser

interpretado en trminos de la teora de OMs

Los orbitales frontera

HOMO/LUMO
definen la qumica de
una especie

+
C

CO es un donador s
y un aceptor p

Una base es un donador de pares de electrones

Un cido es un aceptor de pares de electrones

cido

aducto

base

Los aductos cido-base de Lewis que involucran iones metlicos

se llaman compuestos de coordinacin (o complejos)

La molcula
de NH3

En la mayora de las reacciones cido-base las

combinaciones HOMO-LUMO de los reactivos dan
lugar a nuevos orbitales HOMO-LUMO en el producto
Sin embargo, para que se formen nuevos
orbitales de enlace y antienlace debe haber un
traslape significativo (por simetra) y las
energas deben ser similares

Qu reacciones tienen lugar si las energas son

muy diferentes?

An cuando las simetras sean compatibles, hay muchas reacciones

posibles dependiendo de las energas relativas.

LUMO
HOMO

Si son muy diferentes como A-B A-E

no se forman aductos
Si las energas son similares como en AC A-D se forman aductos

Una base debe tener un par de

electrones en su HOMO con la simetra
adecuada para interactuar con el
LUMO del cido

Hard and soft acids and bases

Hard acids or bases are small and non-polarizable

Soft acids and bases are larger and more polarizable
Halide ions increase in softness:
fluoride < chloride<bromide<iodide
Hard-hard or soft-soft interactions are stronger (with less soluble salts)
than hard-soft interactions (which tend to be more soluble).

Most metals are classified as Hard (Class a) acids or acceptors.

Exceptions shown below: acceptors metals in red box are always soft (Class b).
Other metals are soft in low oxidation states and are indicated by symbol.

Class (b) or soft always

Solubilities: AgF > AgCl > AgBr >AgI

But

LiBr > LiCl > LiI > LiF

Chatts explanationClass (b) soft metals have d electrons available for -bonding
Model: Base donates electron density to metal acceptor. Back donation, from acid to
base, may occur from the d electrons of the acid metal into vacant orbitals on the base.

Higher oxidation states of elements to the right of transition metals have more class b character
since there are electrons outside the d shell.
Ex. (Tl(III) > Tl(I), has two 6s electrons outside the 5d making them less available for -bonding
For transition metals:
high oxidation states and position to the left of periodic table are hard
low oxidation states and position to the right of periodic table are soft

Soft donor molecules or ions that are readily polarizable and have vacant d or * orbitals
available for -bonding react best with class (b) soft metals

Tendency to complex with hard metal ions

N >> P > As > Sb
O >> S > Se > Te
F > Cl > Br > I

Tendency to complex with soft metal ions

N << P > As > Sb
O << S > Se ~ Te
F < Cl < Br < I

The hard-soft distinction is linked to polarizability, the degree to which a molecule

or ion may be easily distorted by interaction with other molecules or ions.
Hard acids or bases are small and non-polarizable
Soft acids and bases are larger and more polarizable
Hard acids are cations with high positive charge (3+ or greater),
or cations with d electrons not available for -bonding
Soft acids are cations with a moderate positive charge (2+ or lower),
Or cations with d electrons readily availbale for -bonding
The larger and more massive an ion, the softer (large number of internal electrons
Shield the outer ones making the atom or ion more polarizable)
For bases, a large number of electrons or a larger size are related to soft character

Hard acids tend to react better with hard bases and soft acids with soft
bases, in order to produce hard-hard or soft-soft combinations
In general, hard-hard combinations are energetically
more favorable than soft-soft

An acid or a base may be hard or soft

and at the same time it may be strong or weak
Both characteristics must always be taken into account
e.g. If two bases equally soft compete for the same acid,
the one with greater basicity will be preferred
but if they are not equally soft, the preference may be inverted

Fajans rules
1.
2.
3.
4.

For a given cation, covalent character increases

with increasing anion size.
For a given anion, covalent character increases
with decreasing cation size.
The covalent character increases
with increasing charge on either ion.
Covalent character is greater for cations with non-noble gas
electronic configurations.

A greater covalent character resulting from a soft-soft interaction is related

With lower solubility, color and short interionic distances,
whereas hard-hard interactions result in colorless and highly soluble compounds

IA

2
Dureza Absoluta
(Pearson)

Blandura

IA

2
Electronegatividad absoluta
de Mulliken (Pearson)

EHOMO = -I
ELUMO = -A

Energy levels
for halogens
and relations between
, and HOMOLUMO energies

Hard-Soft Acid-Base
Concepts

Hard Lewis acids tend to combine

with hard Lewis bases, and soft Lewis
acids tend to combine with soft Lewis
bases
The important properties to consider
in the classification of Lewis acids and
bases are electronegativity, size and
charge; the key features of many of
our deliberations.

Soft Acids

heavy metal ions

insoluble chlorides
chemically inert
fairly electronegative (1.9 - 2.54)
large size (> 90 pm)
low charge (+1 or +2)

Hard Acids

most metals
electronegativity between 0.7 and
1.6
small (<90 pm)
often highly charged (3+ or higher)

Soft Bases

C, P, As, S, Se, Te, Br, I donor atoms

electronegativity between 2.1 and
2.96
radius > 170 pm

Hard Bases

O, F donor atoms
very high electronegativity
r ~ 120 pm
typical examples are sulfate,
carbonate,
silicate, acetate, alcohols, ketones

Principle of Maximum
Hardness

Reacting molecules will arrange their

electrons so as to be as hard as
possible (the electrons are more
tightly held to the atoms and are
therefore less polarizable).
Generally, hard molecules are those
with large HOMO-LUMO gaps, and soft
molecules are those with small
HOMO-LUMO gaps.

Relative Softness

The relative softness of soft acids can

be estimated from the distance of
the acid from Au, the softest atoms.
For 1st row metals, the 2+ state is
borderline,the 3+ state is clearly
hard and the 1+ state (only observed
for traditional coordination
complexes as Cu(I)) is soft.
Acids get softer as they get heavier.

Relative Softness

The softest bases are those with the

lowest electronegativity and lie along
the metal-nonmetal border.
Donor atom softness is also
influenced by the substituent atoms
in bases like phosphines and arsine.

Example of the use of the HSAB

Principle

Predicting to which side and

equilibrium lies:

Catio
n

Typ
e

Why

Nb5+

hard High electronegativity and

charge

Hg2+

soft

Low electronegativity and

charge; closer to Au

Example of the use of the HSAB

Principle

Anion Typ
s
e

Why

S2-

Lower
electronegativity,
large

O2-

soft

Hard High
electronegativity,
products are
favored since
small

Therefore,
they match hard with hard and soft with soft.

Strength and Softness

We need to characterize acid-base

behavior with two parameters (at
least)
We have addressed strength with Z2/r
and other considerations
The general strength rule is that the
strongest acid reacts with the
strongest base, and the weakest acid
reacts with the weakest base.