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In 1968, G. Klopman quantified Pearson's HSAB principle using frontier molecular orbital
(FMO) theory. (The Klopman equation is discussed, here. ) Klopman proposed that:
Hard [Lewis] Acids bind to Hard [Lewis] Bases to give charge-controlled
ionic complexes
and
Soft [Lewis] Acids bind to Soft [Lewis] Bases to give FMO-controlled
covalent complexes
This graphic is captured from The Chemical Thesaurus, here. There are a
number of examples of this type in this reaction chemistry database.
Problems...
However, there is a problem.
While the Pearson-Klopman HSAB model is not "wrong"... it does grossly oversimplify the
reaction chemistry. The reason is that no physical parameter correlates with hardness over
Pearson's chosen set of species.
And as a result, the model introduces ambiguities. How similar are:
Pearson's hard Lewis acids: [NH4]+
H+
CO2
Cs+
Cu2+
R2S:
benzene
Even more importantly, the interesting hard-soft interactions and complexations are simply not
discussed by Pearson's model. What about:
Sodium hydride
Lithium aluminium hydride
Lead(IV) acetate
Methyl lithium
Borane-THF
Triethyloxonium tetrafluoroborate
Ferrocene
The one-dimensional hard-borderline-soft continuum or Pearson's analysis actually has
the effect of blurring much of the rich, linear (predictable) behaviour which can be
found in Lewis acid/base reaction chemistry space.
The chemogenesis analysis, here, avoids and explains the pitfalls of the
Pearson approach.