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HSAB Part 2 - Underlying Theories - 1968
HSAB Part 2 - Underlying Theories - 1968
Ralph G. Pearson
Northwestern University
Evonston, Illinois 60201
HSAB, Part II
Underlying theories
It must he emphasized again that the phosphorus, arsenic, sulfur, or iodine. Also, unsatu-
HSAB principle is intended to he phenomenological in rated ligands such as carbon monoxide and isonitriles
nature. This means that there must he underlying would be able to accept metal electrons by means of
theoretical reasons which explain the chemical facts empty, but not too unstable, molecular orbitals. Class
which the principle summarizes. It seems certain that (a) acids would have tightly held outer electrons, but
there will be no one simple theory. To explain the also there would be empty orbitals available, not too
stability of acid-base complexes, such as A:B, will re- high in energy, on the metal ion. Basic atoms, such as
quire a consideration of all the factors which determine oxygen and fluorine in particular, could form s honds in
the strength of chemical bonds. the opposite sense, by donating electrons from the ligand
Any explanation must eventually lie in the interac- to the empty orbitals of the metal. With class (b)
tions occurring in A:B itself. Solvation effects, while acids, there would be a repulsive interaction between the
important, will not in themselves cause a separation of two sets of filled orbitals on metal and oxygen and
Lewis aeids and hases into two classes, each with its fluorine ligands. Figure 1 shows schematically a p
characteristic behavior. Of course a major part of orbital on the ligand and a d orbital on the metal atom
solventrsolute interaction is itself an acid-base type of which are suitable for forming a honds.
reaction (19). With regard to the bonding in A:B,
several pertinent theories have been put forward by
various workers interested in special aspects of acid-hase
complexation. Figure 1. A p-otomic orbital on a
ligond atom and d orbit01 on a
The oldest and most obvious explanation may be metal atom suitable for r-bond-
called the ionic-covalent theory. I t goes back to the ing. The d orbital is filled and
ideas of Grimm and Sommerfeld for explaining the the p orbital is empty for o soft
odd-loft base rombinotion. The
differences in properties of AgI and NaC1. Hard acids dorbital is empty and theporbitol
are assumed to bind hases primarily by ionic forces. is filled for a herd acid-hard
High positive charge and small size would favor such bore combinmtion. The plus and
minus signs refer to the mothe-
ionic bonding. Bases of large negative charge and moticol sign of the orbital.
small size would be held most tightly-for example,
OH- and F-. Soft acids hind bases primarily by
covalent honds. For good covalent bonding, the two
bonded atoms should he of similar size and similar elec- Pitzer (21) has suggested that London, or van der
tronegativity. For many soft acids ionic bonding Waals, dispersion energies between atoms or groups in
would he weak or nonexistent because of the low charge the same molecule may lead to an appreciable stahiliza-
or the absence of charge. It should be pointed'out that tion of the molecule. Such London forces depend on
a very hard center, such as I(VI1) in periodate or R h - the product of the polarizabilities of the interacting
(VII) in lLlnOa-, will certainly have much covalent groups and vary inversely with the sixth power of the
character in its bonds, so that the actual charge is re- distance between them. These forces are large when
duced much below +7. Nevertheless, there will be a both groups are highly polarizable. It seems plausible
strong residual polarity. to generalize and state that additional stahility due to
The a-bonding theory of Chatt (20) seems particu- London forces will always exist in a complex formed be-
larly appropriate for metal ions, but it can be applied to tween a polarizable acid and a polarizable base. In this
many of the other entries in Table 4 as well. According way the affinity of soft acids for soft bases can be partly
to Chatt the important feature of class (b) acids is con- accounted for.
sidered to be the presence of loosely held outer d-orbital 11ulliken ( B )has given a different explanation for the
electrons which can form a bonds by donation to suit- extra stability of the bonds between large atoms-for
able ligands. Such ligands would be those in which example, two iodine atoms. It is assumed that d-p-
empty d orbitals are available on the basic atom, such as orbital hybridization occurs, so that both the s-bonding
molecular orbitals and the T*-antibonding orbitals con-
The first part of this article appeared on p. 581 of the Sep- tain some admixed d character. This has the two-fold
tember issue of THIS JOURNAL and disccmed the fundmnental
principles of the law of Hard and Soft Acids and Baes. Numbers effect of strengthening the bonding orbital by increasing
of equations, footnotes, and references follow consecutively those overlap and weakening the antibonding orbital by de-
in Part I. creasing overlap.
Volume 45, Number 10, October 1968 / 643
Table 5. Calculated Softness Character (Empty Frontier
Orbital Energy) of Cations and Donors"
Desolva-
Orbitd tionb
energy energy EL
Ion (eV) . .
(eVI
AP+ 6.01'
Laa+ 4.51
Ti'+ 4.35
Be'+ 3.75
Mg'+ 2.42
Figure 2. Atomic orbital hybrids for la) bonding and (b) ontibonding Ca2+ 2.33,
Fez+ 2.22 Hard
molecular orbitolr These atomic hybrids are farmed by combining a 4 p
and o 5 d orbital on each bromine atom. The hybrids are then combined SrP+ 2.21
to form lhe molewlor orbital%. CrS+ 2.06
Bas+ 1.89
Gas+ 1.45 .
Cr2+ 0.91
FeP + 0.69
Figure 2 shows the appearance of the hybrid orbitals Li +
on two bromine atoms. These are now added and sub- H+ Borderline
tracted in the usual way to form bonding and anti-bond- Nia+
Na +
ing molecular orbitals. The bonding orbital will clearly cu2+ -0.55
have a greater overlap than if it were formed by adding TI + -1.88
a p atomic orbital from each bromine atom. Hence it Cd4+ -2.04
Cu' -2.30
will be more bonding. The anti-bonding molecular
8'.
orbital will overlap less than if it were formed by sub-
stracting two p atomic orbitals. Hence it will be less
anti-bonding.
Au
Hg'+
+
-2.82)
-3.37
-4.35
-4.64 I Soft
quite insoluble in methanol. Dithiooxalate salts are bined, as well as soft Cs+ and soft I-, is much more
quite soluble. Benzene would be a very soft solvent, stable than the mismatched combination of hard and
containing only a basic function, however. Aliphatic soft LiI and CsF. However, simple lattice energy con-
hydrocarbons are rather soft complexes, but have no siderations show that i t is the high stability of LiF
residual acid or basic properties to help solvate solutes. (solid) which drives the reaction. The weakly bound
The solvation of cations by water is of paramount im- CsI is just along for the ride, so to speak.
portance in determining the electromotive series of the In addition to solubility of salts, the tendency to form
metals. If one examines the series, one finds at the salt hydrates can he discussed from the HSAB view-
bottom of the list in reactivity the metals Pt, Hg, Au, point. To form a hydrate, we generally need a cation
Cu, Ag, Os, Ir, Rh, and Pd. All of these form soft or an anion which is hard, so that it has an affinity for
metal ions in their normal oxidation states. Their soft- HzO. However, if both the cation and anion are hard,
ness is responsible for their lack of chemical reactivity in the lattice energy will be too great and a hydrate will not
aqueous environment. form.
This can be seen by breaking up the process The alkali halides provide a nice example. We find
M(s) - M t ( a q ) + e- En (22) the greatest tendency to form hydrates with LiI, and
least with LiF, which is rather insoluble, in fact. At the
M(s) -
into three hypothetical parts:
M(d
other end, we find that CsF is one of the few simple
cesium salts which does form a hydrate, whereas CsI
does not. I n the latter case, both ions are soft and,
even though the lattice is weak, water has no tendency
to enter.
the first two of these require energy: the heat of sub- The simple chemical reaction in eqn. (26) is an ex-
limation and the ionization energy, respectively. Only tremely informative one. Let us examine it in an-
the third step gives energy back to drive the entire pro-
cess. If the hydration energy is relatively weak, the
metal will have a low E o value and be unreactive. Soft
LiI(g) + CsF(g) -
other way, by converting to the gas phase.
LiF(g) + CsI(g) (27)
I n this case the heat of the reaction is - 17 kcal, so it is
metal ions will indeed have a low hydration energy still strongly favored to go to the right as shown.
compared to the energy requirements of the first two Again the strong bond between Li and F is decisive.
steps. This is of interest because Pauling ($9)has a celebrated
This suggests that these unreactive metals may be rule for predicting the hcats of reactions such as in eqn.
made reactive by using a different environment: a (27). According to this rule, a reaction is exothermic if
softer solvent or mixture of solvents. It is clear that in the products contain the most electronegative element
a mixed solvent, metal ions of different hardness or soft- combined with the least electronegative element.
ness will sort out the mixture. For example, in very Since Cs is more electronegat,ive than Li, this rule p r o
concentrated solutions of chloride ion in water, hard dicts that reaction (27) will be endothermic!
ions such as Mg2+and Ca2+will bind to H20, whereas Pauling's rule is supposed to be a quantit,at,ive one."
softer ions such as Ni2+, Cu2+,Zn2+,and Cd2+will bind
to C1- ($6). Adding chloride ions to water should in- "owever, it is not considered to be quite as reliable for bonds
crease the reactivity of soft metals more than the reac- between two atoms of greatly different electrol~egativities.