Chap 1 - The HSAB Principle
Chap 1 - The HSAB Principle
Chap 1 - The HSAB Principle
INTRODUCTION
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
Table 1.1 Cohesive Energies of Some Binary Metal Oxides and Sulfides
Mg Ca Ni Zn Pb Ca Cd Hg
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
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
Hard Soft
H", R"
Borderline
(1.3)
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
ORDER OF HARDNESS
Actually chemistry is usually not based on Reaction (1.1), but on the exchange
reaction
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:
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
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.
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
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
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
(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
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
(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)
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
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
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):
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):
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.
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.
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
Comparing Reactions (1.22) with (1.21), it appears that silicon is less affected
than carbon by clustering. But consider the reaction
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
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
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.
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)
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.
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
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•
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
log k [M- ]
Base CH3F CH 3 I
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
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
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
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
C 2 H 5 OH A CH3CHO + H 2 (1.39)
metal
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:
Applied to the exchange reaction (Equation (1.16)), the Pauling equations gives
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
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
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