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Ralph G. Pearson
Northwestern University
Evanston, Illinois 60201
I HSAB, Part I
I Fundamental principles
According to G. N. Lewis a base is an base water forming t,he solvated ion. The chloride ion
atom, molecule, or ion which has at least one pair of also forms an acid-base complex, via hydrogen bonding
valence electrons which are not already being shared in a in which water molecules are 1,ewis acids.
covalent bond. An acid is similarly a unit in which at Inorganic compounds, as solids, liquids, gases, or in
least one atom has a vacant orbital in which a pair of solution, are examples of acid-base complexes. The
electrons can be accommodated. The typical acid- same t.hing can be said for organic compounds. The
base reaction is met,hod here is to ment,ally dissect, t,he organic molecule
into two fragments, one of which is a 1,ewis acid and
the other a base. For example, ethyl alcohol can be
The species A:B may be called a coordination com- thought of as composed of t,he ethyl carbonium ion,
pound, an adduct, or an acid-base complex. I n fact, C2Hs+, and the hydroxide ion, OH-. All carbonium
a wide variety of acid-base complexes exist under dif- ions are Lewis acids and the hydroxide ion is the base.
ferent names. The species A is usually called a Lewis Similarly, ethyl acetate, can be thought of as a com-
acid, or a generalized acid, to avoid confusion with plex of the acylium ion, CH3CO+, which is an acid,
Brfinsted acids. A Lewis base, B, is identical with a and t.he base ethoxide ion, CZH50-. Even a hydrocar-
Brfinsted base. bon can be broken down (conceptually) into an acid
Sidgwick suggested the terms electron acceptor, in such as H + and a carbanion, which is a base. Thus
place of Lewis acid, and electron donor, in place of methane can be considered to be H + and CHI- com-
base. These terms are widely used, particularly in bined. It is equally t,rue that CHI can be viewed as a
Europe. Also certain types of weak generalized acid- combination of CH3+and H-. Such ambiguity is, in
base interactions are almost always discussed under the fact, universal among both organic and inorganic
heading of donor-acceptor complexes. The disad- molecules. While at first confusing, it turns out to be
vantage is that a different term, electron donor, is absolutely necessary to explain the variety of reactions
used to describe substances which are generally and undergone by these molecules. That is, methane some-
conveniently called bases. It is also true that special times reacts as if it were splitting into CH8+ and H-,
names are sometimes used for special categories. The and sometimes as if it were splitting into CHa- and H f .
use of the term ligand in place of base when A in eqn. In addition, there are reactions in which it behaves as
(1) is a metal ion is firmly established. Also in speak- CH3' and H ' . These are redox, or free radical reac-
ing of rates of reaction it is usual to call A an electro- tions, however, and do not concern us here.
phile and to call B a nucleophile.' I n the case of ethyl acetate, the molecule can be
Probably the most important class of chemical reac- viewed as an acid-base complex as explained above.
tion is the generalized acid-base reaction of eqn. (1). It is also true that it is a Lewis acid and a Lewis base.
The easiest way to appreciate this is to consider the Ethyl acetate acts as a Lewis base when it forms com-
different kinds of acid-base complexes, A:R, that may plexes through one of its oxygen atoms to the proton,
be formed. For example, all metal atoms or ions are or other Lewis acids. I t acts as a Lewis acid when it
Lewis acids. They are usually found coordinated to adds bases, such as the hydroxide ion, to its carbonyl
several bases or ligands simultaneously since they are group. Such acid-base processes are important in the
polyvalent. The combination m+y be electrically acid and base catalyzed hydrolyses of esters.
charged, in which case we have a complex ion formed. I t should be noted that a certain group of atoms is
Also the combination may be electrically neutral in often designated as an acid or base even if it has no
which case a normal inorganic molecule such as SnCli is stable existence. A carbonium ion such as CH3+ is
formed. considered to be a Lewis acid because its structure
Most cations are T,ewis acids and most anions are shows that it can accept a pair of electrons from a base.
bases. Hence salts are automatically acid-base com- The breaking down of a molecule, such as CH3C1, into
plexes. MgClz in the solid state consists of the acid a methyl carbonium ion and a chloride ion is a purely
Mg2+coordinated to six neighboring C1- ligands. In di- conceptual process and has nothing to do with the stabil-
lute solution the magnesium ion is coordinated to the ity of CH3f. The point is that most reactions of
methyl chloride can be classified as being exchanges of
EDITOR'SNOTE: This is a two part article. The second the chloride ion by other bases, or of the methyl cat-
part, which discusses the theorys underlying the HSAB principle,
will appear in the October issue. ion by other Lewis acids. Just as the proton does not
HAYEK,E., Osters. Chem-Zenl., 63, 109 (1962), has a general exist free under ordinary circumstances, so it is likely
discussion of the problem of acid-base terminology. that CH3+does not ordinarily exist as a free species.
Volume 45, ~ u m b ; r 9, September 1968 / 581
This brings up the point that equ. (1) is oversimpli- strength factor for the base. Equation (5) is not the
fied. What actually occurs in most cases is the ex- only equation that might result, but it wonld be the
change reaction simplest one that would correctly predict the direction
A:B'+ A ' : B S A : B + A ' : B ' (2)
of displacement reactions such as (3) and (4). Of
course, SA and Se would he functions of the environ-
In solution A' and B' are often solvent molecules. ment and the temperature. The "intrinsic" strengths
Thus, as already mentioned in the case of ions dis- wonld presumably refer to gas phase reactions. There
solved in water, most solute-solvent interactions can would then be strong solvent corrections, but even so
be classified as generalized acid-base reactions. A polar an eqnation such as eqn. (5) would be most useful
molecule will always have an electron rich, or basic since a series of SA and SB values would need to be de-
site, and an electron poor, or acid site. termined once and for all in water at 25"C, and the
Other kinds of acid-base complexes are the so-called stabilities of possible complexes would be known in
charge transfer complexes which are responsible for the that medium. SA and SB values for 100 acids and 100
colors produced when many substances are mixed. bases wonld predict the stabilities of 10,000 complexes,
An example is iodine and the intense brown color it for e ~ a m p l e . ~
gives in solvents which are bases, such as water, alco- Unfortunately it is not possible to write down any
hols, or ethers. Many charge transfer complexes are
formed between Lewis acids which are unsaturated
- ~. If a series
universal order of acid or base strength (B).
of different bases, B', are used in testing against a fixed
molecules with electron-withdrawing substituents, such reference A:B, then the order of base strength that one
as tetracyanoethylene, and unsaturated molecules with gets is very much a function of the nature of the refer-
electron donating substituents, snch as toluene. These ence acid, A. When A is the chromic ion, one gets a
systems are called r-acids and r-bases, respectively. different order from the case when A is the cuprous
Finally, free atoms and radicals containing electro- ion. In fact, the order is different for cupric ion and
negative elements act as Lewis acids and form com- for cuprons ion so that even a change in oxidation state
plexes with a variety of bases. These complexes of of the reference acid can have an effect on relative base
free radicals cannot be isolated but they have a very strengths.
great effect on the reactivity of the radicals. We are forced to the conclusion that there is no
It is apparent that it is possible, in principle a t least, straight-forward way of evaluating base strengths or
to view the greater part of chemistry as examples of acid strengths even if we were to agree that only gas
interaction of generalized acids and bases. This in phase data for reaction (1) be used. Of course, a useful
turn means that any rules that can be developed con- scale of hase strengths towards the special Lewis acid,
cerning the stability of complexes A.B in reaction (1) the proton, in aqueous solution does exist. It must
will have very wide application and can he useful in always be remembered that this scale is not valid for all
many areas. Recently a rule has heen suggested, Lewis acids. It can be useful in a general sense, how-
"The Principle of Hard and Soft Acids and Bases," or ever, in telling us that some bases snch as Clop-, are
HSAB principle, which does seem to have value in un- very weak, and other bases, such as H-, are very strong.
derstanding a wide variety of chemical phenomena (1). Such a rough ordering will usually be valid if two hases
of widely different strengths are being compared.
A comparable scale to order Lewis acids in aqueous
Acid and Base Strength solution has not been devised, partly because many
Lewis acids are decomposed by water. For many
The concept of acid or hase strength comes in a t this others, a scale in which the hydroxide ion is a reference
point. In a qualitative way, what is meant by general- base could be used. In aqueous solution we could write
ized acid or hase strength is simply that a strong acid, both the reactions
A, and a strong base, B, will form a stable complex,
A:B. A weaker acid and hase will form a less stable H+(aq) + B(ad f BHt(aq) (6)
complex. Operationally we may define generalized OH-(aq) + A(aq) + AOH-(aq) (7)
acid and base strength by competition experiments. Any arbitrary value of SA could be assigned to the pro-
Consider the acid-base substitution reactions ton. Let us pick 9.0, for example. This would lead
A1+A:B-Af:B+A (3) to values of Ss ranging from about 5 for a strong base
B'+A:B-A:B'+B (4) snch as CHa- to -1 for a weak base such as I-. The
value of SB for the hydroxide ion wonld then be (15.74/
If the reactions go as indicated, it means that A' is a 9) = 1.75. The number 15.74 is the log10 of the equi-
stronger Lewis acid than A, and that B' is a stronger librium constant for eqn. (6) when B is the hydroxide ion
base than B. If it were possible to put all Lewis acids (55.5/1.0 X 10-14).
into an order of decreasing strength, and the same for This value for SB of OH- then leads to values of SA
all bases, then i t would he possible to predict the stabil- of 5.9 and 8.6 for the aqueous Hg2+and CH3+, respec-
ities of all possible acid-base complexes. That is, we tively. These figures come simply from the acid
could predict what chemical reactions would occur nn- ionization constants of Hg(H20)22+ and CH30H2+ap-
der various conditions, what compounds would be plied to reaction (7). Again, such numbers are useful
stable, etc.
We might then expect the equilibrium constant of
eqn. (1) to be given by an eqnation such as 'One might ask at this point why standard free energies of
formation are not used as the fundamental properties. The
log K = SASB (5) answer is that these involve prior knowledge of the stability of
A:B. We are seeking a method that predicts the properties of
where SA is a strength factor for the acid and SB is a A: B from a knowledge of A and B only, in a given medium.