Hard and Soft Acids and Bases
• 1965- Ralph Pearson introduced the hard-soft-acid-
base (HSAB) principle.
• Hard acids prefer to coordinate the hard bases and soft
acids to soft bases”
• This very simple concept was used by Pearson to
rationalize a variety of chemical information.
• 1983 – the qualitative definition of HSAB was
converted to a quantitative one by using the idea of
polarizability.
• A less polarizable atom or ion is “hard” and a more
easily polarized atom or ion is “soft”
• Hard acid:
• High positive charge
• Small size
• Not easily polarizable
• Hard base:
• Low polarizability
• High electronegativity
• Not easily oxidized
• Soft acid:
• Low positive charge
• Large size; easily oxidized
• Highly polarizable
• Soft base:
• High polarizability
• Diffuse donor orbital
• Low electronegativity
• Easily oxidized
Hard and soft acids and bases
Hard acids or bases are small and non-polarizable
Soft acids and bases are larger and more polarizable
Halide ions increase in softness:
fluoride < chloride<bromide<iodide
Hard-hard or soft-soft interactions are stronger (with less
soluble salts) than hard-soft interactions (which tend to be
more soluble).
Hard acids tend to react better with hard bases and soft acids with soft
bases, in order to produce hard-hard or soft-soft combinations
In general, hard-hard combinations are energetically
more favorable than soft-soft
An acid or a base may be hard or soft
and at the same time it may be strong or weak
Both characteristics must always be taken into account
e.g. If two bases equally soft compete for the same acid,
the one with greater basicity will be preferred
but if they are not equally soft, the preference may be inverted
Fajans’ rules
1. For a given cation, covalent character increases with increasing anion size.
2. For a given anion, covalent character increases with decreasing cation size.
3. The covalent character increases with increasing charge on either ion.
4. Covalent character is greater for cations with non-noble gas
electronic configurations.
A greater covalent character resulting from a soft-soft interaction is related
With lower solubility, color and short interionic distances,
whereas hard-hard interactions result in colorless and highly soluble compounds
HSAB Concepts
• Using HSAB guidelines, reactions between acids and bases can be
often be predicted successfully (though not always)
Q: Is OH- or S2- more likely to form an insoluble salt with a +3 transition metal
ion?
A: The harder species will bind more strongly. Between OH- or S2-, OH- is the
harder species.
Electronic Factors
STABILITY OF COMPLEX
Q: Why is AgI(s) very water-insoluble, but LiI very water-soluble?
A: AgI is a soft acid-soft base combination, while LiI is hard-soft. The
interaction between Li+ and I- ions is not strong.
AgI(s) + H2O(l) essentially no reaction
LiI(s) + H2O(l) Li+(aq) + I-(aq)
Ambidentate Bases
• SCN- (thiocyanate) can interact through either its S or N atom with
Lewis acids. It can donate an electron pair through more than one
atom.
• Interaction will be through the S-atom with a soft acid, or through the
N-atom when interacting with hard acids.
• Cr(III) interacts as Cr-NCS, while Pt(II) does so as Pt-SCN
Electronic Factors
Inductive Effects
• Electron donating substituents
enhance base strength and
electron-withdrawing groups
enhance electron acceptor Me
P
Me H
P
H
(acid) strength Me H
PMe3 stronger base than PH3
gas-phase
base strengths NMe3 > NHMe2 > NH2Me > NH3
strongest base weakest base
This plays a role in bond lengths also
Me = methyl; alkyl, aryl groups are electron donating; F, CF3, CN, etc. are e- withdrawing
