Chap 1 - The HSAB Principle

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1 The HSAB Principle

INTRODUCTION

The concept of chemical, as opposed to physical, hardness appeared in chemistry


in 1963.l It arose in connection with a study of the generalized acid-base reaction
of G. N. Lewis,

A + :B = A:B AH° (1.1)

where A is a Lewis acid, or electron acceptor, and B is a base, or electron donor.


Since the acid-base complex, A: B, can be an organic molecule, an inorganic
molelcule, a complex ion, or anything that is held together by even weak chemical
bonds, the scope of Equation (1.1) includes most of chemistry.
Any insight into the properties of A and B that create a strong bond, or a large
value of —A/f°, would be very useful. It was well known that there is no single
order of acid strength, or base strength, that would be valid in all cases. "Strength"
here is used in the sense of bond strength: that is, a strong acid and a strong base
will form a strong coordinate bond. Indeed, it is fortunate that there is no single
order, since then most of chemistry would already have been done or would
be predictable.
The earliest observations leading to the concept of chemical hardness go back
to the time of Berzelius. It was noted that some metals occurred in nature as their
sulfide ores, and some as their oxides or carbonates. We can show this more
quantitatively by listing the cohesive energies, —A//°, for some binary metal
oxides and sulfides, MO and MS (Table 1.1).

MX(s) = M(g) + X(g) AH° [kcal/mol] (1.2)

The cohesive energy of the oxides is always greater than that of the sulfides.
But the amount, A, by which it is greater can vary with the metal. Thus A is as
large as 54 kcal/mol for Mg and as small as 1 kcal/mol for Hg. It is easy to see
why Mg and Ca occur as carbonates, and Hg and Cd occur as sulfides. The
oxides, of course, would be converted to the carbonates by CO2 in the air.
More recent foundations for the concept of chemical hardness lie in the works
of Chatt2 and Schwarzenbach.3 Independently, they showed that metal ions

Chemical Hardness. R. G. Pearson


Copyright© 1997 WILEY-VCH VerlagGmbH, Weinheim
ISBN: 3-527-29482-1
The HSAB Principle

Table 1.1 Cohesive Energies of Some Binary Metal Oxides and Sulfides

Mg Ca Ni Zn Pb Ca Cd Hg

AH°, MO [kcal/mol] 239 254 219 174 158 178 148 96


AH°, MS [kcal/mol] 185 222 189 147 137 160 132 95

A [kcal/mol] 54 32 30 27 21 18 16 1

could be divided into two classes, (a) and (b), depending on the relative affinities
for ligands with various donor atoms, in aqueous solution.

Class (a) N > P > As > Sb Class (b) N < P > As > Sb
O > S > Se > Te O < S > Se - Te
F > Cl > Br > I F < Cl < Br < I
Edwards had done something similar even earlier.4 His classification, however,
depended on the proton basicity and ease of oxidation of various ligands. He also
made the important step of comparing rates of reaction of various substrates with
the same ligands. The existence of two classes of electrophiles was clearly shown.
Metal ions were simply one group of electrophiles. Class (a) metal ions reacted
most rapidly, and more strongly, with nucleophiles which were very basic to the
proton. Class (b) metal ions reacted most rapidly with nucleophiles that were
easly oxidized. Metal ions are also one class of Lewis acids. The ligands with
which they form complexes are simply Lewis (and Bronsted) bases.
Thus it would be possible to classify other Lewis acids as class (a) or (b).
Because of a shortage of information on formation constants in water, it is
necessary to use a variety of other experimental data. Putting the donor atoms of
bases in order of increasing electronegativity gives
As<P<Se<S~I~C<Br<Cl<N<O<F
The criterion used is that class (a) acids form more stable complexes with the
donor atoms to the right, and class (b) acids prefer donor atoms to the left. This
is essentially the same criterion used by Schwarzenbach and Chatt. Often the
existence or non-existence of related compounds, or complexes, could be used as
an indicator. Rates of reaction could also be used by considering the activated
complex to be an acid-base complex, A: B.
Table 1.2 shows the result of this classification, as presented initially.1 It also
shows that classes (a) and (b) were renamed as "hard" and "soft", respectively.
There are two reasons for this change in nomenclature. One is that it is
often useful to employ comparative terms for two acids, such as "Hg 2+ is softer
than Pb 2 + ". The other comes about as a result of thinking about the funda-
mental properties of a given acid which made it class (a) or (b). The acceptor
Introduction

Table 1.2 Classification of Lewis Acids

Class (a)/Hard Class (b)/Soft

H + , Li+, Na+, K+ Cu+, Ag+, Au + , T1+, Hg+, Cs+


Be 2+ , Mg 2 + , Ca 2 +, Sr 2+ , Sn 2+ Pd 2 + , Cd 2+ , Pt 2+ , Hg 2 +
Al 3 + , Se 3+ , Ga 3 + , In 3 + , La 3+ CH 3 Hg+
Cr 3+ , Co 3 + , Fe 3 + , As 3 + , Ir 3+ Tl 3 + , T1(CH3)3, RH 3
Si 4+ , Ti 4 + , Zr 4+ , Th 4 + , Pu 4+ , VO 2+ RS + , RSe + , RTe +
UO 2 + , (CH3)2Sn2+ I+, Br+, H O + , RO+
BeMe2, BF 3 , BC13, B(OR) 3 I 2 , Br2, INC, etc.
A1(CH3)3, Ga(CH 3 ) 3 , In(CH 3 ) 3 Trinitrobenzene, etc.
RPO+,ROPO+. Chloranil, quinones, etc.
RSO+, ROSO+, SO 3 Tetracyanoethylene, etc.
I 7 + , I 5 + , Cl 7+ O, Cl, Br, I, R 3 C
R 3 C+, RCO+, CO 2 , NC+ M° (metal atoms)
Bulk metals
HX (hydrogen-bonding molelcules)
Borderline
Fe 2 + , Co 2 + , Ni 2 + , Cu 2 + , Zn 2 + , Pb 2 +
B(CH 3 ) 3 , SO2, NO+

atoms of the first class are usually of high positive charge and small size, with no
unpaired electrons in the valence shell. Class (b) acids have acceptor atoms of
low positive charge and large size, and often have unshared pairs of electrons in
the valence shell. These characteristics meant that class (a) acceptor atoms are
not very polarizable, whereas class (b) acceptor atoms are very polarizable.
Since polarizability means deformation of the electron cloud in an electric
field, and since things that are easily deformed are soft, this leads to the two
classes of acids being called hard and soft, respectively. What one really has in
mind is deformation in the presence of other atoms or groups to which bonding
was occurring. Thus optical polarizability, although a useful measure of softness,
is not quite the correct measure.
Looking at the list of donor atoms for bases given above, it is obvious that
polarizability is high on the left side and diminishes as one goes to the right. By the
same argument as before, bases which donor atoms such as As, P, Se, S or I are
called soft bases. Bases with F, O and N are hard bases. A hard base has an
electron cloud that was difficult to deform chemically. Electrons were held tightly,
so that loss of an electron is difficult, whereas a soft base is easily deformed and
even oxidized. Table 1.3 shows some typical examples.
With this new nomenclature it is possible to make a simple, general statement:
"Hard acids prefer to coordinate to hard bases, and soft acids prefer to coordinate
soft bases." This is the Principle of Hard and Soft Acids and Bases, or the
HSAB Principle.
The HSAB Principle

Table 1.3 Classification of Bases

Hard Soft

H 2 O, OH", F " R 2 S, RSH, RS~


CH 3 CO^, POJ", SOj" I", SCN", S 2 O|"
Cl", COf", CIO4, NO3- R 3 P, R 3 As, (RO) 3 P
ROH, RO", R 2 O CN", RNC, CO
NH 3 , RNH 2 , N 2 H 4 C2H4, C6H6

H", R"

Borderline

C 6 H 5 NH 2 , C5H5N, N3-, Br", NO^, S O ^ , N 2

Note that this Principle is simply a restatement of the experimental evidence


which led to Table 1.2. It is a condensed statement of a very large amount
of chemical information. As such it might be called a law. But this label seems
pretentious in view of the lack of a quantitative definition of hardness. HSAB is
not a theory, since it does not explain variations in the strength of chemical
bonds. The word "prefer" in the HSAB Principle implies a rather modest effect.
Softness is not the only factor which determines the values of AH° in Equation
(1.1). There are many examples of very strong bonds between mismatched pairs,
such as H2, formed from hard H + and soft H~. H2O, OH~ and O2~ are all
classified as hard bases, but there are great differences in their base strength, by
any criterion.
Obviously, all of the factors which determine bond energies must be taken into
account, such as the charges and sizes of A and B, the electronegatives of the
donor and acceptor atoms, orbital overlaps, and steric repulsions. The HSAB
Principle then refers to an additional stabilization of hard-hard or soft-soft
pairs, or a destabilization of hard-soft pairs.
For convenience, let us adopt the modern symbols 77 (Greek eta = h) and
a (Greek sigma = s) for chemical hardness and softness, respectively. The
relationship between the two is a = I/77. Also, let us lump all other factors
determining the strength of bonds formed by A and B into a single factor, SA or SB,
"intrinsic" strength.5 Thus S& is larger for OH" than for H2O.
If there were a single order of strengths for acids, and for bases, then SA and
SB could be defined by equations such as

(1.3)

The HSAB effect then might be added by the modification

-AH° = SASB + aAaB (1.4)


Order of Hardness 5

where the a terms could be positive numbers for soft species and negative
numbers for hard species.
One could, of course, attempt to use Equation (1.4) by taking one set of data to
assign values of S&, S&, a\ and <JB to a number of acids and bases, and then using
another set of data to check them. Actually something similar to this has already
been done by Drago and Wayland, with their well-known four-parameter
equation.6

-AH° = EAEB + CACB (1.5)

Here EA and EB measure ionic bonding and CA and CB measure covalent


bonding. This is appropriate, since in looking for the reasons underlying the
HSAB effect, it is clear that hard-hard interactions are mainly ionic and soft-soft
interactions are mainly covalent.7 But there are many other effects, such as
repulsions due to the overlap of filled atomic orbitals on A and B.8 For this and
other reasons, E and C may not be good measures of S and a. A disadvantage of
Equation (1.5) is that different numbers are needed for different environments.

ORDER OF HARDNESS

Actually chemistry is usually not based on Reaction (1.1), but on the exchange
reaction

A : B + A': B' = A : B' + A': B' (1.6)

The following conclusion can then be drawn, provided A and A' are acids of the
same strength, or B and B' are bases of the same strength:

hs + sh = hh + ss 0 > AH° (1.7)

where h and s are read as the harder and softer of the two acids (bases).
Equation (1.7) is the result of applying Equation (1.5) to the four acid-base
complexes contained in reactions (1.6). The strength terms cancel out, and the a
terms give the value of AH°. Now it is not practical to demand that S\ = SA' or
SB = SBS but it is possible to ensure that they be comparable in magnitude. This
can be done by requiring that A and A' be acids of the same charge, and of
similar size, and the same for B and B'. This minimizes the influence of the SASB
terms, and enhances the CFA<JB terms.
Equation (1.7) is based on Equation (1.5) but does not require numbers for its
application, only the relative hardnesses of the reactants. But these can be
obtained by applying Equation (1.7) to a set of related data. Turning back to
6 The HSAB Principle

cohesive energies, we can assume that the metal ions are all acids of comparable
strength. The cohesive energies of all the oxides are larger than those of the
sulfides because the oxide ion is a stronger base, due to its smaller size.
Similarly, the value of AH° for MgO is larger than that for HgO because Mg 2+
is smaller than Hg 2+ . Nevertheless, the strengths are comparable, not grossly
different as they would be, say, for Al 3+ and K + . Accordingly, Equation (1.7)
enables us to write the order of increasing softness as

Mg 2+ < Ca 2+ < Ni 2+ < Zn 2+ < Pb 2+ < Cu 2+ < Cd 2+ < Hg 2+

using the values of A and the reasonable assumption that the sulfidle ion is softer
than the oxide ion.
By comparing only acids of the same charge, and bases of the same charge, we
have the great advantage that the predictions of Equation (1.7) are not sensitive
to the environment.

CaS(s) + CuO(s) = CaO(s) + CuS(s) AH° = -14 kcal/mol (1.8)

CaS(g) + CuO(g) = CaO(g) + CuS(g) AH° = -30 kcal/mol (1.9)

Also we see from Table 1.2 that in aqueous solution Cu 2+ is softer than Ca 2+ .
Indeed, Table 1.2 is in agreement with the ordering above, but with less detail for
the various metal ions.
A further check on the hardness ordering can be made using a different set of
reference reactions. The bond dissociation energies of fluorides and iodides were
used in the earliest attempt to order the metal ions:9

MF2(g) = M(g) + 2F(g) AH°F (1.10)

MF2(g) - M(g) + 2F(g) AHf (1.11)

Defining A as AH? - AHf, we find the same order of A as before, and assuming
that I" is softer than F~, the same order of increasing softness.
Note that even though we are considering the reactants to be M 2+ and F~ or
I~5 it is possible to use ordinary bond energies because only differences are
important. Table 1.4 gives the empirical hardness order for a number of singly
charged Lewis acids, based on the bond dissociation energies of fluorides and
iodides, Z>F and Df.10 We see that SiH^ is the hardest acid of this group,' followed
by CF^. In accordance with Table 1.2, Cu + , Ag + and OH + are very soft acids.
The same kind of analysis may be made to rank a series of bases in order of
increasing softness. Because of the large amount of data, it is convenient to use
H + and CHjj" as the reference acids, with H + being the harder. Table 1.5 gives the
hardness order for a number of singly charged anions, using A = Z>H — ^CH 3 as
the criterion. As expected, F " and OH~ are the hardest bases. Simple carbon
ions are much softer, e.g., CH^ and C 6 H 5 CH^.
Order of Hardness

Table 1.4 Empirical Hardness Parameters for Cationic


Lewis Acids (a)

Acid Z)p [kcal] A° [kcal] A [kcal]

SiH+ 150 71 79
CF+ 130 54 76
CH 3 CO + 120 50 70
HCO+ 122 52 70
H+ 136 71 65
C6H+ 124 64 60
C 2 H^ 119 63 56
t-C4H+ 108 50 58
i-C3H+ 107 53 54
C2H+ 107 53 54
CH+ 109 56 53
C 3 Ht 98 44 54
c-C3H+ 111 59 52
Li + 137 82 55
Na + 123 69 54
T1+ 105 64 41
CN+ 112 73 39
N0+ 56 20 36
Cs+ 118 82 36
1+ 67 36 31
Cu + 102 75 27
Ag + 87 61 26
HO+ 56 52 4

(a)
After Reference 10.

The cyanide ion is an ambident base. The carbon end is seen to be much softer
than the nitrogen end, as would be predicted. The greater strength of the H-CN
bond, compared with H-NC, means that the carbon end is much more basic
than the nitrogen end. This would be true even in solution, since the ions are the
same for both acids. As a result, binding to carbon will be more common than
binding to nitrogen, even for hard acids.
Tables 1.4 and 1.5 contain acids or bases with a wide range of acceptor or
donor atoms. In such cases, use of different references will not give identical
orderings. Usually the variations are not very great, being shifts of two soft, or
two hard, acids or bases with respect to each other.10'11
The most reliable (i.e., transferable) results are obtained if two similar acids or
bases are used as references. Thus OH~ and SH~ will give the same ordering as
F~ and I~, but H~ and F~ will give orders that are quite different: the alkali
metal cations will be much harder than in Table 1.4. Such changes in order are
evidence for special bonding effects in certain A: B combinations.
The HSAB Principle

Table 1.5 Empirical Hardness Parameters for Anionic


Bases(a)

Base Dk [kcal] 1Ota, [kcal] A [kcal}

F" 136 109 27


cr 103 85 19
Br- 88 70 18
I- 71 56 15
OH" 119 92 27
SH- 91 74 17
SeH~ 79 67 12
NH2 107 85 22
PH2- 87 76 11
AsH 2 75 63 12
CH 3 CO^ 106 83 23
C 6 H 5 O" 87 64 23
NOJ 102 80 22
CH 3 O- 104 83 21
HO2 88 69 19
ONO- 78 60 18
NO2- <78 61 <17
NCS" 96 77 19
C 6 H 5 NH- 88 71 17
n-C 3 H 7 S- 87 72 15
C 6 H 5 S- 83 69 14
CH3- 105 90 15
SiH^ 91 89 2
GeH3- 87 83 4
C6H5CH2 88 72 16
NCCH^ 93 81 12
CH3COCH2~ 98 86 12
C3H5 86 74 12
QH5 111 100 11
C2H3 110 105 5
HC2 130 122 8
CH 3 CO" 96 91 5
CF3- 106 101 5
CN- 124 122 2
NC- 110 98 12
H" 104 105 -1

(a)
After Reference 1

In the case of H~, the special effect is the total absence of 7r-bonding or 7r-anti-
bonding. Hydride ion is a pure a-donor, compared with iodide ion. Figure 1.1
shows the 7r-interaction of a d (or p) orbital on an acceptor atom, and a p (or d)
orbital on a donor atom. If the d orbital is filled, and the p orbital is empty, there
is a stabilizing effect. This would be the case in a soft-soft A: B complex. If the
Order of Hardness

^Lc—r>- M -«<--

Figure 1.1 A p orbital on a ligand atom and a d orbital on a metal atom. The plus and minus
signs refer to the mathematical signs, or phases, of the orbitals in different regions of space.

d orbital is empty, and the p orbital is filled, there would also be a stabilization,
as in a hard-hard combination. If both the d and p orbitals are filled, there would
be a destabilization, as in a hard-soft combination.
These 7r-bonding effects are part of the theory of the HSAB Principle. We can
also imagine that London dispersion energies between atoms or groups in an A: B
complex could stabilize it. Since these dispersion energies, or van der Waals
energies, depend on the product of the polarizabilities of the two groups, soft-soft
combinations would be stabilized in this way. The hydride ion is very polarizable,
and its softness depends on this factor, presumably.
Because of the absence of 7r-orbital effects, the bond strength of HX, where X is
any element, depends almost entirely on the clectronegativity of X. D° ranges from
42kcal for CsH to 136kcal for HF, for the Main-Group elements. For the

1100

900

DC 700

500

300

100
2
XP

Figure 1.2 Plot of force kR0 [kcal/mol A] against the Pauling electronegativity of X, for HX
molecules. Reprinted from R.G. Pearson, J. Mol. Struct. (Theochem.), 300, 519 (1993), with
kind permission of Elsevier Science - NL, Sara Burgerhartstraat 25, 1055 KV Amsterdam,
The Netherlands.
10 The HSAB Principle
Table 1.6 Comparison of Na + and Cu+ as Lewis Acids

Reaction A//° [kcal/mol]

NaH(g)=Na+(g) + H~(g) 151


NaF(g)=Na+(g) + F"(g) 163
CuH(g)=Cu+(g) + H-(g) 222
CuF(g)=Cu+(g) + F"(g) 202
H~(g) 403
F"(e) 371

transition metals, the range is more variable because of the necessity to promote to
the valence state (half-empty s orbital).13 Promotion energies are also important
for the hydrides of Groups 2 and 12.
Figure 1.2 shows kR0 plotted against the Pauling electronegativity, Xp> f° r all
the diatomic hydrides where the data is available. The quantity kR0, where k is
the force constant and Ro the internuclear distance, is simply the force that the
atom X exerts on the H atom.13 This force is a good measure of what the bond
energy would be without the interference of promotion energies.
As expected, H + is also a rather special Lewis acid because of the absence of
filled inner shells. Consider the reactions in Table 1.6. The results show that Cu +
is a "stronger" acid than Na + , though the "strengths" are comparable. This
accords with copper being more electronegative than sodium. The numbers also
show clearly that Cu + is softer than Na + . The proton is seen to be a very strong
acid because of its small size and ability to burrow into the electron cloud of
bases. There is no destabilization with the soft hydride ion in H 2 . Note that
hydride ion is a strong base, comparable with fluoride ion.

SOLVATION ENERGIES

As mentioned earlier, a method for classifying Lewis acids is based on relative


equilibrium constants in water for the formation of complexes. Hydration
energies must play an important role. As Table 1.4 shows, F~ forms a stronger
bond to all cationic acids in the gas phase than I~ does. But because the hydration
energy of F~ is 50kcal greater than for I~, inversions in A7/°, and in formation
constants, can occur for acids like Ag + , but not for CH 3 CO + .
For solvents less polar than water, the difference in the heats of solvation will
usually be less than 50 kcal, and inversions in order will not occur. Thus, even for
Rh(I) and Pt(II) the order Cl > Br > I is found in most non-aqueous solvents. But
this is not a violation of the HSAB Principle.
Solvation Energies 11
Table 1.7 Bond Dissociation Energies for M : B + = M + -f : B in the
Gas Phase (a)

M:B+ AH° [kcal/mol] M:B+ AH°

Ag(H2O)+ 29.2 Li(H 2 O) + 36


Ag(H 2 S) + 32.4 Li(H 2 S) + 25
Ag(H 2 Se) + 34.8 Li(H 2 Se) + 24.5
Ag(NH 3 ) + 43.3 Li(NH 3 ) + 41
Ag(PH 3 ) + 40.5 Li(PH 3 ) + 27
Ag(AsH3)+ 25.4 Li(AsH 3 ) + 23
Ag(HF)+ 16.3 Li(HF)+ 23.5
Ag(HCl) + 18.2 Li(HCl)+ 18.0
Ag(HBr)+ 21.0 Li(HBr)+ 17.0

(a)
Data from Reference 14.

For neutral molecules acting as bases, the effect of solvents would be similar to
that of ions, but smaller in magnitude.1 That is, a hard acid solvent like water
would deactivate other hard molecules more than related soft molecules. Table 1.7
lists the calculated bond dissociation energies for a number of complexes in the
gas phase

AH0 (1.12)

The numbers are theoretical ones, but the method of calculation used gives very
good agreement with experiment, where numerical results have been obtained.15
It might be thought that the slightly stronger bonding in Ag(NH 3 ) + than in
Ag(PH3)+ is a failure of the HSAB Principle, since Ag + is soft. But this
overlooks the requirement that data in aqueous solution are to be used. Since the
heats of hydration of NH 3 and PH 3 are —8.1 kcal/mol and —3.6kcal/mol, the
difference is enough to overcome the small difference in bond energies for Ag +
(2.8 kcal/mol), but not enough for Li + (19kcal-mol).
The HSAB Principle can also be tested by applying equation (1.7):

Ag(NH3)+(g) + Li(PH3)+(g)

= Ag(PH3)+(g) + Li(NH3)+(g) AH° = -16 kcal/mol (1.13)

This test works for all the examples in Table 1.2, and also for similar data for
Na + compared with Ag + . 16
Table 1.8 has some data on the proton affinities (PA) of a number of neutral
molecules:

-AH° = PA (1.14)
12 The HSAB Principle

Table 1.8 Gas-phase Proton Affinities


of Some Neutral Bases(a)

Base PA [kcal/mol]

HF 117
H2O 167
NH 3 205
CH 4 121
HC1 135
H2S 170
PH 3 189
HBr 139
H2Se 171
AsH 3 179

(a)
Data from Reference 16.

The results for H 2 O, H2S and H2Se are surprising and would not have been
anticipated in 1963, when few data on PAs were known. The strength of bonding
increases with the size of the donor atom, even though the base strength is not
expected to increase, and the softness does increase. The opposite trend should
have been observed, as it is for NH 3 , PH 3 and AsH3. The hydrogen halides show
an even greater reversal.
Neither Equation (1.4) nor Equation (1.7) can explain these results. It is a gas-
phase phenomenon, since it vanishes in solution, where the expected orders are
found for H2O, H2S and H2Se.16 The simplest explanation is that the inverted
order is the result of the classical charging energy for a sphere. This energy (the
Born charging energy) is given by

AE = q2/2eR (1.15)

where q is the charge, R the radius of the sphere, and e the dielectric constant of
the medium.
In more detail, since the proton in Equation (1.14) bears a positive charge, the
energy increase results from the repulsion of the proton by the shielded nuclear
charges of B. These are largest for a short bond to the proton, as we have in
H 3 O + , and are lower for H 3 S + and H 3 Se + . Also the nuclear repulsions decrease
as charge is removed from the nucleus to the outer parts of the molecule, as in
going from H 2 F + to N H j . Since Equation (1.15) depends inversely on R, the
overall effect is to make small molecules reluctant to add protons in the gas phase.
This is unfortunate, since there is a great deal of data available on the methyl
cation affinities (MCA) of neutral molecules17

B(g) + CH3+(g) = BCH3+(g) -AH° = MCA (1.16)


Complex Ions in Water 13

Comparison of MCAs with PAs, as in Equation (1.14), could lead to a hardness


ordering of neutral molecules, just as was done for anions in Table 1.5. But small
molecules, which are usually hard, will appear too soft because of the Born
charging energies. This problem does not arise for anionic bases.

COMPLEX IONS IN WATER

Complex formation between metal ions and ligands in aqueous solution has
always been of great interest. This interest is enhanced by the role of metal ions
in biology. The first use of the concept of chemical hardness was to explain
complex ion formation in water. However, it turns out that this is not so easy as
one might expect.
There is a great deal of data available, not only on equilibrium constants, but
also on heats of reaction between metal ions and various ligands.18 For various
practical reasons, it is difficult to find data that can be used even in a comparative
sense. Solvation energies are one obvious problem. Only for restricted cases can
we use Equation (1.7).
Nevertheless, some useful generalizations may be made. Consider the typical
reaction for the formation of a complex in water (charges are omitted for
simplicity):

MLw(H2O)(aq) + Y(aq) = MLnY(aq) + H2O(1) (1.17)

There are four interactions in Equation (1.17) which are acid-base in character.
One is the interaction of MLW with H 2 O, the second is the MLW interaction with Y,
the third is the interaction of Y with the solvent, and the fourth is the interaction
of water with itself, a constant factor. The solvation energies of the large complex
ions, MLW(H2O) and MLWY, are governed primarily by the Born equation.
If ML« is hard and Y is soft, or vice versa, we can expect AH° to be positive, or
only a small negative number. Therefore, complexation will not be favorable.
Suppose MLM is hard and Y is hard. Then their interaction will be favorable. But
H2O is a hard molecule, both as an acid and a base. Therefore Y(aq) and
MLW(H2O) are also stabilized. Overall, only a small negative value for AH° can be
hoped for, and moderately stable complexes.
But if ML« is soft and Y is soft, then everything works in favor of a large
negative value for A//°, and very stable complexes. Ahrland has made a detailed
study of the available data and has found a remarkable agreement with the above
predictions.19 Hard acids rarely form complexes with soft bases, and hard bases
do not form very stable complexes with soft acids, except for strong bases such
as OH".
14 The HSAB Principle

Hard acids form only moderately stable complexes, even with hard bases, and
AH° is close to zero. Soft acids and soft bases usually form very stable complexes
in aqueous solution, and AH° is then a large negative number. For a soft reference
acid, such as Pd 2+ or CH 3 Hg + , the order of increasing values of -AH° is
F" <C Cl- < Br- ~ N j < I" < SCN" < RS~ < CN". 18 " 20 For neutral ligands
the order is H2O < NH 3 < thiourea < PR3. Note that the order for anions is not
exactly the same as in Table 1.5 because of different hydration energies.
There are not enough comparable data to put many metal ions in rank order,
but the following orders of decreasing values of -AH° can be established:
Hg 2+ > Cd 2+ > Zn 2+ ; Pt 2+ - Pd 2+ > Ni 2+ . Also the Irving-Williams order21
for formation constants of complexes, V 2+ < Cr2+ > Mn 2+ < Fe 2+ < Co 2+ <
Ni 2+ < Cu 2+ > Zn 2+ , follows the experimental values of rj for these metal ions.
As expected, the magnitude of the changes in log^ e q increase with the
polarizability of the ligand donor atoms.22
There is an excellent recent review of the role of metal ions in biology by
Hancock and Martell.23 The discussion is in terms of HSAB, but for quantitative
work the most accurate treatment is by an equation related to Equation (1.5):

l o g * ! = E'AE'B + C'AC'B - DADB (1.18)

K\ is the equilibrium constant (in H 2 O, at 25 °C) for Reaction (1.1), and the E1
and C parameters are analogous to those in Equation (1.5), but are empirical
numbers from data in water.24
The D parameters are necessary to account for steric effects. The last term in
Equation (1.19) can be neglected for large cations, but is important for small
cations. It emphasizes another important difference between reactions in solution
and in the gas phase. In solution the Lewis acid is multicoordinate, and has a
number of water molecules attached to it. The steric effects arise from clashes of
the ligand with these water molecules. A large number of E\ C and D
parameters are now available, and can be used to estimate formation constants
for complexes between metal ions and the common ligands.

SYMBIOSIS AND ANTI-SYMBIOSIS

In Table 1.3, BF3 is listed as a hard acid but BH3, which also contains B(III), is
considered a soft acid. For example,25

BH 3 : NH 3 + BF 3 : CO
- BH 3 : CO + BF 3 : NH 3 AH° = -12kcal/mol (1.19)
Symbiosis and Anti-symbiosis 15

Also, in Table 1.4, CFj is shown as a harder acid than CH3". These are examples
of a very general phenomenon, first noted by Jorgensen and called by him the
"symbiotic" effect.26 Soft bases attached to the same central acceptor atom make
it a soft acid, and hard bases make it a hard acid. In coordination chemistry,
symbiosis explains why some ligands, such as CN~ or phenanthroline, make a
metal ion form strong complexes with other soft ligands, whereas F~ and H2O
favor the bonding of other hard ligands.27
The symbiotic effect is also common in organic chemistry, but here it has been
called the clustering, anomeric, or geminal effect.28'29 Clustering refers to the
stabilization caused by adding several substitutents to the same carbon atom.
Some extreme examples are shown by Reactions (1.20) and (1.21), in which the
number of bonds of each kind is preserved.

4CH3F(g) = 3CH4(g) + CF4(g) AH° = -63 kcal/mol (1.20)

4CH3OCH3(g) - 3CH4(g) + C(OCH3)4(g) AH° = -52 kcal/mol (1.21)

In Reaction (1.20) the comparison is between F~ and H~, the hardest and softest
bases in Table 1.5, and the effect is at a maximum.
Elements other than carbon may be influenced, for example29'30

4SiH3F(g) = 3SiH4(g) + SiF4(g) AH° = -23 kcal/mol (1.22)

Comparing Reactions (1.22) with (1.21), it appears that silicon is less affected
than carbon by clustering. But consider the reaction

SiF3H(g) + CF4(g) = SiF4(g) + CF3H(g) AH° - -37 kcal/mol (1.23)

Clearly SiFjj" is much harder than CF^, just as SiHjj" is harder than CHj. An
extreme example of the difference between the two elements is given by

C(OCH3)4(g) + SiH4(g)
= CH4(g) + Si(OCH3)4(g) AH° = 144 kcal/mol (1.24)

This illustrates the great affinity of silicon for binding to oxygen donors.
Organic chemists usually explain the anomeric effect by double-bond-no-bond
resonance.29 This is consistent with the observation that F~, OR~ and NR^
bases give the largest effects. However, the HSAB principle provides a much
simpler explanation. The acceptor atom in BF3, CF3" and SiF^ is much more
positive than in BH3, CH 3 and SiH^. Since a high positive charge enhances
hardness (Table 1.3), we now have acids which bind better to hard bases, such
as F~, than to soft bases such as H~.
In spite of this simple and logical explanation, there are many cases of anti-
symbiotic behavior for the soft metal ions of the second and third transition
16 The HSAB Principle

series.31 That is, soft bases attached to a soft acid center, such as Ir(I), Hg(II),
Pt(II) and Au(III), can lower the affinity for another soft base. But this only
occurs for a coordination site trans to the original ligand. The rule is that two
soft ligands in mutual trans positions will have a destabilizing effect on each
other, when attached to a soft metal ion.31
This rule explains a host of experimental observations. For example,
(CH3)2Hg is readily cleaved by dilute acid to form linear CH 3 Hg(H 2 O) + . But
this cation resists cleavage, even by strong mineral acids. There is a simple
explanation based on the theory of the trans effect.32 This effect occurs only for
soft metal ions, and ligands of high trans effect are always soft ligands.
The theory of the effect postulates that the bonding in such cases is largely
covalent. Ligands in trans positions compete for the same orbitals to form
covalent bonds (a or TT). Therefore it is advantageous to have a hard ligand, such
as H2O or OH~, trans to each soft ligand already attached.33 Anti-symbiosis
should be minor in tetrahedral complexes, or when the acceptor atom is hard.

NUCLEOPHILIC REACTIVITY

Early evidence for the HSAB Principle came from studies of nucleophilic
reactivity series towards different substrates, or electrophiles.34 Some electro-
philes, such as H + , in proton transfer reactions or CH 3 CO + substitution
reactions of esters, reacted rapidly with bases that were strong bases towards the
proton. Other electrophiles, such as Pt(II) or RO + , reacted rapidly with
polarizable bases, and were indifferent to proton basicity.
It soon became clear that these two classes should be called hard and soft
electrophiles, respectively. Since the terms nucleophile and electrophile refer to
rates of reaction, by definition, the acid-base reaction involved is

B' + A:B = B ' : A : B ^ B ' : A + B (1.25)

The rate then depends on the stability of the activated complex B7 : A : B. This,
in turn, depends mainly on the compatiblity of B' and A, if relative rates for a
series of nucleophiles, B', are compared.
Figure 1.3 shows the rate constants for the hydrolysis of/?-nitrophenyl acetate,
catalyzed by the attacks of bases on the carbonyl carbon.35 There is a rough
proportionality between log k and pKa. The scatter is expected when a number of
bases of different natures are compared. While F~ is fairly reactive, Cl~, Br~ and
I~ show no measurable reactivity.
In contrast, Figure 1.4 shows rate data for many nucleophiles reacting with a
pyridine (Pyr) complex of Pt(II) in methanol at 25 °C.36

B + trans-Pt(pyr)2Cl2 ^ /r<ms-Pt(pyr)2ClB+ + Cl" (1.26)


Nucleophilic Reactivity 17

Figure 1.3 Rate constants for the reactions of nucleophiles in aqueous solution at 25 °C,
plotted against the basicities of the attacking reagents. After Reference 35.

The rate constants are shown as a parameter, n, defined as

n = log(k/ks) (1.27)

where ks is the rate constant for solvolysis. The plot is that of n against the pKa in
water, but using pKa values in methanol, when known, makes no difference.
Clearly there is no dependence of n on the normal proton basicity. In fact
CH3O~, the strongest base possible in methanol, has no detectable reaction with
trans-Pt(pyY)2Cl2. The same is true for F~, but Br~ and I~ are good reagents.
An important substrate for nucleophilic reactivity is methyl iodide. This serves
as a model for substitution reactions at tetrahedral carbon in general, the
SN2 reaction

B + CH3I A CH 3 B + + I (1.28)

The greatest amount of rate data is in methanol at 25 °C.36 The values of n


range from n = 0 for the solvent, to n = 10.7 for C6H5Se". Some organometallic
18 The HSAB Principle

10 -
9 - o cP

8 -
o
7 - 0

6 - o
o
5 o
o
4 - o o o
o o
3 o

2 -
? ? ° ?
1 1 1

-8 -6 -4 -2 0 2 4 6 8 10 12 14 16

Figure 1.4 Plot of npt, in CH 3 OH, against pKa in H 2 O. After Reference 35.

anions, such as Fe(CO)4~ and (C5H5)Fe(CO)^, react even faster.37 A plot of n


against pKa shows behavior intermediate between that in Figures 1.3 and 1.4.
Both CH3O~~ and I~ are good reagents. The best reagents are all soft bases, and
the overall picture is that CH^ is a moderately soft electrophile. This is consistent
with Tables 1.3 and 1.4.
The values of n cannot be used as an order of increasing softness, since that
would ignore the "intrinsic strength" factor. To emphasize the strength factor, it
is useful to examine the equilibrium constant for Reaction 1.28. For anionic
bases, X~,

X-(aq) + CH3I(aq) = CH3X(aq) + r ( a q ) -AGC (1.29)

There are enough data available to calculate AG° for a large number of anion
bases, and a smaller number of neutral bases, B.37
The order of decreasing values of AG° is H2O > CH 3 OH > Br~ - NO^ > I" >
F~ > Cl- > SCN~ > CH 3 COO (CH3)2S C 6 H 5 O- (CH3)3As
NH 3 > C 6 H 5 S- > n-C 3 H 7 S- O- > (CH3)3P CN~ CH 2 CN-
H~ > CHj > C6H5". The range of equilibrium constants is 60 powers of 10. The
order is that of decreasing thermodynamic leaving-group ability. It is in good
agreement with the kinetic leaving-group ability, the nucleofugality, when known.
The next step is to compare n with AG°. That is, to look for a linear free
energy relationship,. This is usually expressed as38

= aAG° + constant (1.30)

where AG-f is the free energy of activation. Over a wide range of AG°, a need not
remain constant, but it must change slowly and continuously. Figure 1.5 shows a
Nucleophilic Reactivity 19

10r

3 •

1•

0 -12 -24 -36


AG°
Figure 1.5 Plot of n against AG° [kcal/mol] in water at 25 °C, for the reaction of CH 3 I
with nucleophiles. Circles are for first-row donors (F, O, N, C) and crosses for heavier donors.
Key: 1, CN"; 2, CH 3 Cr; 3, HO^; 4, (C 2 H 5 ) 3 N; 5, piperidine; 6, pyrollidine; 7, N 2 H 4 .
Reproduced with permission from R.G. Pearson, J. Org. Chem., 52, 2131 (1987). ©1987
American Chemical Society.

plot of n, which is proportional to AG-f, against AG° for the cases where n is
known. First-row donors (F, O, N, C) are shown as circles and higher-row
donors as crosses. The former all lie close to the smooth curve that has been
drawn. The latter all lie above it.
The curve acts as a reference line, but it also shows that the slope, a, in
Equation (1.30) has a value near one for AG° near zero, and approaches zero as
AG° becomes a large negative number. Such behavior is an expected consequence
of the Bell-Evans-Polanyi-Leffler-Hammond principle.39 It corresponds to a
late transition state for the more difficult reactions and a progressively earlier
transition state for more exergonic reactions. However, the curve appears to level
off at an n value near 8, which corresponds to a second-order rate constant of
about 1 M" 1 s~! at 25 °C, far from the diffusion-controlled limit.
Recent developments, both experimental40 and theoretical in nature,41 help
explain this behavior. The energy barrier to reaction consists of a part that exists
in the gas phase and in solution, and a solvation part found only in solution. The
20 The HSAB Principle

gas-phase barrier exists because five groups attached to carbon in the transition
state are at a higher energy than four. The solvation barrier results because the
nucleophile must be partly desolvated before it can react, and the transition state
(TS) must be solvated. For the reaction of Cl~ with CH3C1, the two parts are of
comparable magnitude in water, each being about 14kcal/mol. Desolvation of
Cl~ requires more energy than is returned in solvating the TS.
For neutral nucleophiles the situation is somewhat different. The gas-phase
energy barrier is very large, so that reactions such as (1.28) simply do not occur.
For example, when B is NH 3 we have

NH3(g) + CH3I(g) = CH3NH+(g) + r (g) AG°(g) = 108 kcal/mol (1.31)

Obviously only strong solvation of the polar TS allows Reaction (1.21) to go


with a measureable rate in solution.
The estimation of the gas-phase energy barrier is difficult for anions, even
when the rate constants are available. However, we can be reasonably sure that
this barrier gets smaller as AG°(g) becomes a more negative number. For OH~,
CH3O~, HO2 and CN", AG°(g) is -64, -57, -62, and-48kcal/mol, respect-
ively. It is likely in these cases that the gas-phase barrier has become negligible,
and only the solvation barrier remains. This would account for the leveling off of
the rate constants shown in Figure 1.5. The limiting rate constant corresponds to
a value of AG-f of about 20 kcal/mol, which is reasonable. The scatter of the n
values for these four anions would then be due to variations in the solvation
energy barrier. For neutral nucleophiles, the gas-phase barrier can become
smaller, but it can never become negligible. Therefore no leveling off will occur.
The n values for such nuclelophiles, in fact, continue to rise as AG° becomes
more negative in Figure 1.5.
We turn next to the crosses in Figure 1.5 which refer to donor atoms other
than ones in the first row. It is seen that all the crosses are well above the
reference curve, indicating greater reactivity than is predicted by the AG° values.
The maximum deviation, about 7.5kcal, is shown by I~. These reactive
nucleophiles are all soft, whereas all the first-row donors in Figure 1.2, except
CN~, are hard nucleophiles. The deviations shown by the crosses are examples of
the rule "softness is more important in rates than in equilibria."
By comparing AG+ with AG°, we hope to have accounted for the dramatic
effect of the solvent on lowering the reactivity of hard bases. Looking at Reaction
(1.25), it appears that the enhanced reactivity of soft bases must be accounted for
by favorable interactions between B and B' in the TS, B': A: B. But this is just
the symbiotic effect, since the leaving group, B, is iodide ion, which is soft. The
existence of this symbiotic effect on rates has been known for some time.42
We can predict that the enhanced reactivity of soft bases will vanish if B is a
hard base, such as F~. The data for reaction in H2O show just such an effect
(Table 1.9).43 The same large decreases occur when the leaving group, B, is
sulfate, nitrate or sulfonate, all hard O-donors.
Other Applications 21

Table 1.9 Values of log k for Reaction


of Bases in Water

log k [M- ]

Base CH3F CH 3 I

H2O -10.8 -8.9


OH- -6.1 -4.3
ci- -8.6 -5.5
I- -7.7 -3.5

The easiest way to identify symbiosis is to examine a ratio such as


which will be large for soft nucleophiles and small for hard ones. A convenient
probe is an ambident nucleophile which usually has a hard site and a soft site. An
example is Me2SO, which reacts at oxygen with methyl benzenesulfonate and at
sulfur with methyl iodide. These changes in selectivity have been found in all
solvents, including dipolar, aprotic ones.44
Such additional stabilization should appear in the gas-phase energy barrier.
This is difficult to demonstrate because of the large effect of exothermicity, and
because the stabilization is usually small. For example, in the gas-phase reactions
of CH3CI with CH3O" and CH3S~, the barrier height is 2.6 kcal/mol higher for
the soft CH3S~40. The reaction with CH3O~ is 13kcal/mol more exothermic,
which could reduce its barrier by 5-6 kcal/mol, relative to CH3S~. The expected
TS stabilization is only about 3 kcal/mol (see above), which is not inconsistent.
Symbiotic effects are a serious problem in the use of the Marcus equation to
predict rates of methyl group transfers.45 This otherwise useful equation predicts
that for a pair of reactions such as

CH3X + Y-> CH3Y + X kx (1.32)

CH3Z + Y -* CH3Y + Z kz (1.33)

that the ratio kx/kz should be constant, or nearly so.46 But we have just seen that
the ratio k\/kF can change by a factor of 200 when Y changes fdrom OH~ to I~. In
other cases 47 the ratio changes by as much as 106. The theory behind the Marcus
equation does not allow for interactions between entering and leaving groups.

OTHER APPLICATIONS

In one way or another, the HSAB Principle has found many applications in most
areas of chemistry.48 Usually these depend on the implicit use of Equation (1.7).
22 The HSAB Principle

Unfortunately this equation is as quantitative as HSAB gets. There was no exact


definition of hardness, 77, and no operational definition which allowed it to
be measured. The values in Tables 1.4 and 1.5 are useful only in ordering acids
and bases. They are not transferable as numbers to any other examples. There-
fore applications have always been qualitative. Even so, the HSAB concept
has been extremely useful in correlating and understanding a great deal of
experimental data.
Often this has been done by simply providing another perspective to view a
body of information. Consider the case of the reactivity of metals, as given by the
electromotive series:

K(s) = K + (aq) + e" AE° = 2.93 V (1.34)

Ag(s) = Ag+(aq) + e" AE° = -0.80 V (1.35)

What causes the large difference of 3.73 V, or 86kcal/mol? Let us break the
overall reaction into two parts, one requiring energy and the other giving back:

K Ag
M(s) = M+(g) + e" AHi [kcal/mol]: 120 243
M+(g) = M+(aq) AH2 [kcal/mol]: 79 116
~4T T27

We see that potassium has an energy shortfall of 41 kcal/mol, but silver has a
much larger one of 127 kcal/mol. The difference is equal to the 86 kcal/mol of free
energy given by AE°, since entropy effects nearly cancel. Thus silver is less
reactive than potassium partly because it is harder to ionize, due to greater
electronegativity, but also because it does not interact with the solvent water as
strongly as expected. Since water is a hard base and Ag + is a soft acid, such a
result is reasonable.
Looking at the electronegative series of the elements, we see that the noble
metals, Hg, Au, Pt, Ir, Pd, Os, Rh and Ru, all form metal ions which are
classified as soft. Their heats of hydration are all less than expected and their
inertness is thus explained.
The advantage of this viewpoint is that it focuses attention on the solvent. It
suggests that by changing the solvent, we might invert the reactivities of the
alkali metals, which form hard metal ions, and the Cu, Ag, Au triad. Even more
easily, of course, by adding soft bases such as CN~ to water we can increase the
reactivity of the noble metals.
The whole subject of solubility and solvation energies can be looked at in
HSAB terms. The rule "Similia similibus dissoluntur" can be replaced by "Hard
solvents dissolve hard solutes, and soft solvents dissolve soft solutes". This
Other Applications 23

requires examination of the generalized acid-base properties of solvents. Most


solvents have a donor site and an acceptor site, which may differ widely in both
hardness and strength.
Hydrogen bonding is an acid-base phenomenon. We find that the strongest
hydrogen bonds are formed between hard acids and hard bases, such as H2O and
OH~. The smaller heat of hydration of SH", although explained by simple size
effects, is also consistent with the HSAB viewpoint. The conclusion is that
hydrogen bonding is mainly an electrostatic interaction. This is in contrast to the
Mulliken approach, which stresses charge transfer.
Empirical softness values have been assigned to some 90 common solvents.48
The scale is defined as the difference in the free energy of transfer of a hard cation
(Na + or K + ) from water to a given solvent and the corresponding quantity for a
soft cation (Ag+). The scale can be used in linear solvation energy correlations,
or simply to estimate solubilities.
Stabilization of certain oxidation states for an element can be predicted by
HSAB. For example, to have a Ni(IV) compound, we will need hard ligands, or
counter ions, such as F~ or O2~. To have Ni(0), we need soft ligands, such as
CO, PR3, AsR3 or R2S. The growth of organometallic chemistry of the
transition metals, which was just under way in 1963, was facilitated by realizing
that ligands such as CH^, H~ and C 2 H 4 were all soft, and that they would need
soft metal centers to which to bind. The metal could be made soft by a low
oxidation state, which in turn could be stabilized by other soft ligands.
An unusual property of transition metal hydrides is that they are often quite
strong Bronsted acids.49 A typical example would be
H2Fe(II)(CO)4 = H + + HFe(0)(CO)4 pKa = 4.4 (1.36)

The ionization reaction is also a typical reductive elimination, since the formal
oxidation state of the metal decreases by two units. We can predict that hard
ligands will stabilize Fe(II) in preference to Fe(0), and will reduce the acidity of
H2Fe(CO)6.
This kind of prediction has been amply verified for other cases.49 Consider the
rhodium(III) complexes

Rh(NH3)4(H2O)H2+ pKa > 14


2+
Rh(bipy)2(H2O)H pKa = 9.5
2+
Rh(CNR)4(H2O)H pKa < 0
The effect is quite large, even though the net charges are constant. The order of
increasing 77 is isocyanide < bipyridine (bipy) < ammonia.
Organometallic compounds of the transition metals are involved in many
important examples of homogeneous catalysis, such as the Wacker process and
the oligomerization of olefins. These require that an organic molecule, such as
ethylene, be coordinated to a metal atom holding another potential reactant.
24 The HSAB Principle

A good strategy is to have a hard ligand attached to a soft metal atom. The hard
ligand is often a solvent molecule such as H2O or CH3CN. Since these will be
labile, vacant coordination sites for the organic reactant are readily available.50
Soft ligands, present in the solution, will act as catalyst poisons,
Saville has developed rules for chemical reactions that can also be used to
select homogeneous catalysts.51 Consider the four-center reaction

B' + A:B + A' = B':A + B:A' (1.37)

Reaction is facilitated if A: B is a mismatched pair in terms of hardness, and if


the hardness of B' matches that of A and that of A' matches B. An example
would be the cleavage of ethers by hydrogen iodide:

r + C2H5OC2H5 + H + ^ C 2 H 5 I + C2H5OH (1.38)

The ready hydrolysis of alkyl iodides makes this a catalytic reaction.


Heterogeneous catalysis is made much more understandable by considering
the interactions between the surface atoms of the catalyst and the adsorbed
reactants as acid-base reactions. The two main classes of catalysts are typified by
the transition metals and by the acid clays. The bulk metals have atoms in the
zero-valent state and are all soft acids. They are also soft bases, since they can
donate electrons easily. Catalysts such as Al2O3-SiO2 mixtures contain hard
metal ions as acids, and hard oxide, or hydroxide, ions as bases.
Because of strong adsorption, we expect compounds of P, As, Sb, S and Se to
be poisons for transition metal catalysts. Soft acids such as Hg 2+ and Pb 2+ will
also be poisons. But poisons for the acid clays will be hard metal ions, and hard
bases, such as NH 3 , CO 2 " and SO4".
Differences in reaction products, such as

C 2 H 5 OH A CH3CHO + H 2 (1.39)
metal

C2H5OH -^ C 2 H 4 + H2O (1.40)


clay

are readily accounted for. The metal surfaces remove hydride ions (and return
electrons to the substrate); the acid clay removes H + and OH~.
Pauling's bond energy equation is one of the best-known empirical equations
in chemistry:

£>AB = \ (D°AA + D°m) + 23(XA - XB)2 (1.41)

Pauling used it to assign electronegativity values, XA and XB, to the elements.52


It still often used in various ways, in spite of many publications pointing out its
inaccuracies.
Summary 25

Applied to the exchange reaction (Equation (1.16)), the Pauling equations gives

AH = 46(XA' - XAXXB - XB<) kcal/mol (1.42)

That is, the reaction will be exothermic if the products contain the least electro-
negative (EN) element combined with the most EN element. But this usually is
the opposite of what Equation (1.7) will predict. Take the example

Lil(g) + CsF(g) = Csl(g) + LiF(g) AH = -17 kcal/mol (1.43)

Equation (1.42) gives AH = 46(0.7 - 1.0)(2.5 - 4.0) = +21 kcal/mol.


Equation (1.7) will correctly predict that Reaction (1.43) is exothermic,
assuming that Cs4" is softer than Li + , just as I~ is softer than F~, and as shown in
Table 1.4. Many similar examples can be cited.52 If Equation (1.41) is used along
with Pauling's EN values to calculate A in Table 1.4, there will be errors as large
as 80 kcal/mol.
The limited validity of Equation (1.41) is for bonds where (XA — XB) is small,
that is, for covalent bonds. It is useless for bonds that are highly ionic, as we have
in Reaction (1.43).54 There are improved versions of Pauling's equations
available, which are much better for ionic bonds.55 In spite of these criticisms, the
EN values calculated by Pauling using Equation (1.41) are perfectly reasonable
and are accepted as the standard. This is a tribute to Pauling's insight (and to a
careful selection of data to be used!).

SUMMARY

In retrospect it seems clear that the original concept of hardness and softness is
an example of "fuzzy logic." In spite of its name, fuzzy logic is a respected
branch of mathematics, which was essentially invented in 1965 by L. A. Zadeh. It
is a method of reasoning and making decisions when the available information is
not precise enough to use numbers, or definite statement such as "Yes" or "No."
On the other hand there is some information which is qualitative in nature and
insufficient to make definite statements.
Classical mathematics requires that a concept has a precise definition which
partitions a class of objects into two classes: (a) those that belong, and (b) those
that do not belong. But the real world is filled with concepts such as many, old,
slow, large. These do not have sharply defined boundaries, but still convey
information. Fuzzy logic deals with the application of such knowledge.
As might be expected, there was at first considerable criticism and rejection of
Zadeh's proposals. Today, however, there are many papers being published that
concern the development and application of fuzzy logic. There are a number of
26 The HSAB Principle

important uses already well established, particularly in technology, manufactur-


ing and finance. Applications in science will surely follow. It is of interest to note
the recent appearance of a book entitled Fuzzy Logic in Chemistry.56
Nevertheless, it is a great advantage in science to have quantitative definitions
so that one can measure what one is speaking about, and express it in numbers.
Fortunately this is what has happened to chemical hardness. The means by
which this has come about lies in density functional theory. This will be the topic
of the next chapter.

REFERENCES

1. R.G. Pearson, /. Am. Chem. Soc, 85, 3533 (1963).


2. S. Ahrland, J. Chatt and N.R. Davies, Quart. Rev. (London), 12, 255 (1958).
3. G. Schwarzenbach, Adv. Inorg. Che. Radiochem. 3, 1 (1961).
4. J.O. Edwards, /. Am. Chem. Soc, 76, 1540 (1954).
5. R.G. Pearson, Chemistry in Britain, 3, 103 (1967).
6. R.S. Drago and B.B. Wayland, /. Am. Chem. Soc, 87, 3571 (1965).
7. G. Klopman, /. Am. Chem. Soc, 90, 223 (1968).
8. R.G. Pearson, /. Chem. Ed., 45, 643 (1968).
9. R.G. Pearson and R.J. Mawby, Halogen Chemistry, V. Gutmann, Ed., Academic Press,
New York, 1967, Vol. 3, p.61ff.
10. R.G. Pearson, /. Am. Chem. Soc, 110, 7684 (1988).
11. A.F. Bochkov, Zhur. Org. Khim., 22, 2041 (1986). A.S. Peregrudov et al., J. Organomet.
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Summary 27

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