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Hard and Soft Acids and Bases.
Hard and Soft Acids & Bases
Large, highly polarizable
ions are categorized as
“soft.” Iodide is a soft base,
and transition metals with
low charge density, such as
Ag+, are considered to be
soft acids.
Charge Density – Soft Acids
Soft acids typically have lower charge
density (lower ionic charge and greater
ionic size). Their d orbitals are available
for π bonding. Soft acids are often 2nd and
3rd row transition metals with a +1 or +2
charge, and filled or nearly filled d orbitals.
Hard-Soft Acid-Base Theory
Charge Density – Hard Acids
Hard acids typically have a high charge
density. They are often metal ions with a
(higher) positive charge and small ionic
size. Their d orbitals are often unavailable
to engage in π bonding.
Hard and Soft Acids and Bases.
We have already pointed out that
the affinity that metal ions have for
ligands is controlled by size, charge
and electronegativity. This can be
refined further by noting that for
some metal ions, their chemistry is
dominated by size and charge,
while for others it is dominated by
their electronegativity. These two
categories of metal ions have been
termed by Pearson as hard metal
ions and soft metal ions. Their
distribution in the periodic table is
as follows:
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Hard and Soft Acids and Bases. Hard and Soft Acids and Bases.
Pearson’s Principle of Hard and Soft Acids and
Bases (HSAB) can be stated as follows:

Hard Acids prefer to bond with Hard

Bases, and Soft Acids prefer to bond
with Soft Bases.

This can be illustrated by the formation

constants (log K1) for a hard metal ion, a soft
metal ion, and an intermediate metal ion, with
the halide ions in Table 1:
Figure 1. Table showing distribution of hard, soft, and intermediate Lewis
Acids in the Periodic Table, largely after Pearson.

Table 1. Formation constants with halide ions for a

representative hard, soft, and intermediate metal ion .
_________________________________________________
Hard and Soft Acids and Bases.
hard soft
Log K1 F- Cl- Br- I- classification What one sees in Table 1 is that the soft
_________________________________________________ Ag+ ion strongly prefers the heavier halide
soft-soft interaction ions Cl-, Br-, and I- to the F- ion, while the
hard Fe3+ ion prefers the lighter F- ion to
Ag+ 0.4 3.3 4.7 6.6 soft the heavier halide ions. The intermediate
Pb2+ ion shows no strong preferences
Pb2+ 1.3 0.9 1.1 1.3 intermediate
either way. The distribution of
hardness/softness of ligand donor atoms
Fe3+ 6.0 1.4 0.5 - hard
_________________________________________________
in the periodic Table is as follows:
hard-hard interaction

Distribution of Hard and Soft Bases by

donor atom in the periodic Table: Distribution of Hard and Soft Bases by
donor atom in the Periodic Table.
The hardness of ligands tends to show, as seen
C N O F in Figure 2, a discontinuity between the lightest
member of each group, and the heavier
P S Cl members. Thus, one finds that the metal ion
affinities of NH3 are very different from metal ion
As Se Br
affinities for phosphines such as PPh3 (Ph =
I phenyl), but that the complexes of PPh3 are very
similar to those of AsPh3. A selection of ligands
classified according to HSAB ideas are:
Figure 2. Distribution of hardness and softness for potential donor atoms
for ligands in the Periodic Table.

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Hard and Soft Bases. A very soft metal ion, Au(I):

HARD: H2O, OH-, CH3COO-, F-, NH3, oxalate
(-OOC-COO-), en (NH2CH2CH2NH2).
SOFT: Br-, I-, SH-, CH3S-, (CH3)2S, S=C(NH2)2
(thiourea), P(CH3)3, PPh3, As(CH3)3, CN-
-S-C≡N (thiocyanate, S-bound)
The softest metal ion is the Au+(aq) ion. It is so soft that
the compounds AuF and Au2O are unknown. It forms
stable compounds with soft ligands such as PPh3 and
CN-. The affinity for CN- is so high that it is recovered in
mining operations by grinding up the ore and then
suspending it in a dilute solution of CN-, which dissolves
the Au on bubbling air through the solution:

INTERMEDIATE: C6H5N (pyridine), N3- 4 Au(s) + 8 CN-(aq) + O2(g) + 2 H2O =

(azide), N=C=S (thiocyanate, N-bound), Cl-
-
4 [Au(CN)2]-(aq) + 4 OH-

(donor atoms underlined)

The aurocyanide ion is linear, with two-coordinate Au(I). A very hard metal ion, Al(III):
This is typical for Au(I), that it prefers linear two-
coordination. This coordination geometry is seen in other An example of a very hard metal ion is Al(III). It
complexes of Au(I), such as [AuPPh3CN], for example. has a high log K1 with F- of 7.0, and a
Neighboring metal ions such as Ag(I) and Hg(II) are also reasonably high log K1(OH-) of 9.0. It has
very soft, and show the same unusual preference for virtually no affinity in solution for heavier halides
two-coordination. P such as Cl-. Its solution chemistry is dominated
Au Au by its affinity for F- and for ligands with negative
C N O-donors.

One can rationalize HSAB in terms of the idea

that soft-soft interactions are more covalent,
while hard-hard interactions are ionic. The
a) b) covalence of the soft metal ions relates to their
higher electronegativity, which in turns depends
Typical linear coordination geometry found phenyl on relativistic effects.
for Au(I) in a) [Au(CN)2]- and b) [Au(CN)(PPh3)] group

What one needs to be able to comment on is

sets of formation constants such as the Another set of examples is given by:
following:

Metal ion: Ag+ H+

Metal ion: Ag+ Ga3+ Pb2+

log K1(OH-): 2.0 11.3 6.0 Log K1 (NH3): 3.3 9.2

log K1(SH-): 11.0 8.0 6.0 Log K1 (PPh3): 8.2 0.6
What is obvious here is that the soft Ag+ ion
prefers the soft SH- ligand to the hard OH- Again, the soft Ag+ ion prefers the soft
ligand, whereas for the hard Ga3+ ion the phosphine ligand, while the hard H+
opposite is true. The intermediate Pb2+ ion has
no strong preference.
prefers the hard N-donor.

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Thiocyanate, an ambidentate ligand: Cu(I) and Cu(II) with thiocyanate:

In general, intermediate metal ions also tend to bond to
Thiocyanate (SCN-) is a particularly interesting ligand. It thiocyanate through its N-donors. A point of particular
is ambidentate, and can bind to metal ions either through interest is that Cu(II) is intermediate, but Cu(I) is soft.
the S or the N. Obviously, it prefers to bind to soft metal Thus, as seen in Figure 4, [Cu(NCS)4]2- with the
ions through the S, and to hard metal ions through the N. intermediate Cu(II) has N-bonded thiocyanates, but in
[Cu(SCN)3]2-, with the soft Cu(I), S-bonded thiocyanates
This can be seen in the structures of [Au(SCN)2]- and
are present.
[Fe(NCS)6]3- in Figure 3 below: Figure 4. Thiocyanate
Figure 3. Thiocyanate complexes of the
Complexes showing intermediate Cu(II) ion
a) N-bonding in the and soft Cu(I) ion. At a)
[Fe(NCS)6]3- the thiocyanates are
complex with the hard N-bonded in [Cu(NCS)4]2-
Fe(III) ion, and with the intermediate
b) S-bonding in the Cu(II), but at b) the
thiocyanates in
[Au(SCN)2]- complex
[Cu(SCN)3]2-, with the soft
(CSD: AREKOX) with
Cu(I), are S-bonded
the soft Au(I) ion (CSD: PIVZOJ).

Applications of Hard/Soft
Theory
The Qual Scheme, a series of chemical
reactions used to separate and identify the
presence of dozens of metal ions, is based
largely on the hard and soft properties of
the metal ions.
The softer metals are precipitated out
as chlorides or sulfides, with the harder
ions formed as carbonates.

Evidence in Nature Evidence in Nature

In geochemistry, the elements in the
earth’s crust are classified as lithophiles or
chalcophiles.
The lithophile elements are typically
found as silicates (bonded via the O
atom): Li+, Mg2+, Ti3+, Al3+ and Cr2+,3+.
These are hard Lewis acids.
The chalcophile elements are typically
found as sulfides or bonded to Se2- or Te2-.
They include: Cd2+, Pb2+, Sb3+, and Bi3+.
These are soft Lewis acids. Zinc ion,
which is borderline, is typically found as a
sulfide.

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