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 elctronegativity. 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:
Figure 1. Table showing distribution of hard, soft, and intermediate Lewis Acids in the
Periodic Table, largely after Pearson.
Pearsons Principle of !ard and "oft Acids and #ases $!"A#% 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 K&% for a hard metal ion, a
soft metal ion, and an intermediate metal ion, with the halide ions in Table &:
Table 1. 'ormation constants with halide ions for a representative hard, soft, and
intermediate metal ion .
((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((
Log K& '
)
*l
)
#r
)
+
)
classification
((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((
Ag
,
-.. /./ ..0 1.1 soft
Pb
2,
&./ -.3 &.& &./ intermediate
'e
/,
1.- &.. -.4 ) hard
((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((
&
What one sees in Table & is that the soft Ag
,
ion strongly prefers the heavier halide ions
*l
)
, #r
)
, and +
)
to the '
)
ion, while the hard 'e
/,
ion prefers the lighter '
)
ion to the heavier
halide ions. The intermediate Pb
2,
ion shows no strong preferences either way. The
distribution of hardness5softness of ligand donor atoms in the periodic Table is as follows:
Figure 2. 6istribution of hardness and softness for potential donor atoms for ligands in
the Periodic Table. The diagram shows that hardness increases toward '
)
, and softness
increases away from '
)
. !owever, this is not a smooth transition. There is, as shown, a
ma7or discontinuity between the lighter members of each group, namely, '
)
, 8, and 9,
and their heavier congeners. Thus, *l
)
, #r
)
, and +
)
are far more li:e each other, and far
different from '
)
, in their bonding preferences, as can be seen in Table &.
The hardness of ligands tends to show, as seen in 'igure 2, a discontinuity between the
lightest member of each group, and the heavier members. Thus, one finds that the metal
ion affinities of 9!/ are very different from metal ion affinities for phosphines such as
PPh/ $Ph ; phenyl%, but that the comple<es of PPh/ are very similar to those of AsPh/. A
selection of ligands classified according to !"A# ideas are:
!A=6: !28, 8!
)
, *!/*88
)
, '
)
,

9!/, o<alate $
)
88*)*88
)
%, en.
"8'T: #r
)
, +
)
, "!
)
, $*!/%2", ";*$9!2%2 $thiourea%, P$*!/%/, PPh/, As$*!/%/, *9
)

)
")*>9 $thiocyanate ")bound%
+9T?=@?6+AT?: *1!49 $pyridine%, 9/
)
$azide%,
)
9;*;" $thiocyanate, 9)bound%, *l
)
The softest metal ion is the Au
,
$aq% ion. +t is so soft that the compounds Au' and Au28
are un:nown. +t forms stable compounds with soft ligands such as PPh/ and *9
)
. The
affinity for *9
)
is so high that it is recovered in mining operations by grinding up the ore
and then suspending it in a dilute solution of *9
)
, which dissolves the Au on bubbling air
through the solution:
. Au$s% , A *9
)
$aq% , 82$g% , 2 !28 ; . BAu$*9%2C
)
$aq% , . 8!
)
B&C
2
The aurocyanide ion is linear, with two)coordinate Au$+%. This is typical for Au$+%, that it
prefers linear two)coordination. This coordination geometry is seen in other comple<es of
Au$+%, such as BAuPPh/*lC, for e<ample. 9eighboring metal ions such as Ag$+% and !g$++%
are also very soft, and show the unusual preference for two)coordination.
An e<ample of a very hard metal ion is Al$+++%. +t has a high log K& with '
)
of 0.-, and a
reasonably high log K&$8!
)
% of 3.-. +t has virtually no affinity in solution for heavier
halides such as *l
)
. +ts solution chemistry is dominated by its affinity for '
)
and for
ligands with negative 8)donors.
8ne can rationalize !"A# in terms of the idea that soft)soft interactions are more
covalent, while hard)hard interactions are ionic. The covalence of the soft metal ions
relates to their higher electronegativity, which in turns depends on relativistic effects.
What one needs to be able to comment on is sets of formation constants such as the
following:
@etal ion: Ag
,
Da
/,
Pb
2,
Log E&$8!
)
%: 2.- &&./ 1.-
Log E&$"!
)
%: &&.- A.- 1.-
What is obvious here is that the soft Ag
,
ion prefers the soft "!
)
ligand to the hard 8!
)

ligand, whereas for the hard Da
/,
ion the opposite is true. The intermediate Pb
2,
ion has
no strong preference. Another set of e<amples is given by:
@etal ion: Ag
,
!
,
Log K&$9!/%: /./ 3.2
Log K& $PPh/%:A.2 -.1
Again, the soft Ag
,
ion prefers the soft phosphine ligand, while the hard !
,
prefers the
hard 9)donor.
Thiocyanate $"*9
)
% is a particularly interesting ligand. +t can bind to metal ions either
through the " or the 9. 8bviously, it prefers to bind to soft metal ions through the ", and
to hard metal ions through the 9. This can be seen in the structures of BAu$"*9%2C
)
and
B'e$9*"%1C
/)
in 'igure / below:
/
Figure 3. Thiocyanate comple<es showing a% 9)bonding in the B'e$9*"%1C
/)
comple<
with the hard 'e$+++% ion, and b% ")bonding in the BAu$"*9%2C
)
comple< $*"6:
A=?E8F% with the soft Au$+% ion.
+n general, intermediate metal ions also tend to bond to thiocyanate through its 9)donors.
A point of particular interest is that *u$++% is intermediate, but *u$+% is soft. Thus, as seen
in 'igure ., B*u$9*"%.C
2)
with the intermediate *u$++% has 9)bonded thiocyanates, but in
B*u$"*9%/C
2)
, with the soft *u$+%, ")bonded thiocyanates are present.
Figure 4. Thiocyanate comple<es of the intermediate *u$++% ion and soft *u$+% ion. 9ote
that at a% the thiocyanates are 9)bonded in B*u$9*"%.C
2)
with the intermediate *u$++%, but
at b% the thiocyanates in B*u$"*9%/C
2)
, with the soft *u$+%, are ")bonded $*"6: P+GH8I%.
.