HSAB PRINCIPLE

• The large electronegativity differences between hard acids and hard bases give rise to strong ionic
interactions.

• The electronegativities of soft acids and soft bases are almost same and hence have less ionic
interactions. i.e., the interactions between them are more covalent.

* The interactions between hard acid - soft base or soft acid - hard base are mostly polar covalent
and tend to be more reactive or less stable. The polar covalent compounds readily form either more
ionic or more covalent compounds if they are allowed to react.
Hard and Soft Acids and Bases (HSAB) Principle is a qualitative concept introduced by Ralph
Pearson to explain the stability of metal complexes and the mechanisms of their reactions.

It is also possible to quantify this concept based on Klopman's FMO analysis*

using interactions between HOMO and LUMO.

According to HSAB principle, the Lewis acids and bases can be further divided into hard or soft or
borderline types:

Hard Lewis acids are characterized by small ionic radii, high positive charge, strongly solvated, empty
orbitals in the valence shell and with high energy LUMOs.
Soft Lewis acids are characterized by large ionic radii, low positive charge, completely filled atomic
orbitals and with low energy LUMOs.
Hard Lewis bases are characterized by small ionic radii, strongly solvated, highly electronegative,
weakly polarizable and with high energy HOMOs.
Soft Lewis bases are characterized by large ionic radii, intermediate electronegativity, highly
polarizable and with low energy HOMOs.

The Borderline Lewis acids and bases have intermediate properties.

In short, Hard acids and bases are small and non-polarizable,

whereas soft acids and bases are larger and more polarizable.

*frontier molecular orbital theory is an application of molecular orbital theory describing HOMO–LUMO interactions
Hard small high strongly empty high
Lewis acids positive
Soft large low completely low
Lewis acids positive filled
Hard small strongly highly weakly high.
Lewis bases
Soft large intermediate highly low
Lewis bases
Ionic charge solvated orbitals in electronegative polarizabl energy energy
radii the valence e LUMO HOMO
shell
 HSAB & FMO ANALYSIS

concept based on Klopman's FMO analysis

using interactions between HOMO and LUMO.

According to FMO analysis, the interactions between acids and bases are controlled by the
relative energies of the participating frontier molecular orbitals (FMO) i.e.,
HOMO and LUMO.

Greater the energy gap between the HOMO & LUMO, harder is the species.
Quantitatively the absolute hardness of a species is determined by following equations:
Type of Acid/Base CHARACTERISTICS EXAMPLES

* Atomic centers of small ionic radii (<90 pm). H+, Li+, Na+, K+, Be2+, Mg2+, Ca2+, Sr2+, Sn2+
* High positive charge.
* Empty orbitals in their valence shells. Al3+, Ga3+, In3+, Cr3+, Co3+, Fe3+, Ir3+, La3+, Si4+, Ti4+, Zr4+,
Hard acids * Low electronegativity (0.7-1.6) and low electron affinity. Th4+,U4+, VO2+ , UO22+
* Likely to be strongly solvated.
* High energy LUMO. BeMe2, BF3, BCl3, B(OR)3, AlMe3

* Large radii (>90 pm). Cu+, Ag+, Au+, Hg+ , Cs+ , Tl+ , Hg2+ , Pd2+, Cd2+ , Pt2+
* Low or partial positive charge.
Soft acids * Completely filled orbitals in their valence shells. Metal atoms in zero oxidation states
* Intermediate electronegativities (1.9-2.5)
* Low energy LUMOs with a large magnitude of LUMO BH3
coefficients.
Borderline acids Fe2+ , Co2+ , Ni2+ , Cu2+ , Zn2+ , Pb2+ , B(CH3)3, SO2, NO+

* Small radii (around 120pm) & highly solvated.

* electronegative atomic centres (3.0-4.0). H2O, OH-, F-, Cl-, CH3CO2-, PO43-, SO42-, CO32-, NO3-, ClO4-,
Hard bases * Weakly polarizable. ROH, RO-, R2O, NH3, RNH2, N2H4
* Difficult to be oxidized.
* High energy HOMO.

* Large atoms (>170 pm) with intermediate electronegativity (2.5-

3.0). S2-, RSH, RS-, R2S, I-, CN-, SCN-, S2O3-, R3P, R3As,
Soft bases * High polarizability (RO)3P, RNC, CO, C2H4, C6H6, R-, H-
* Easily undergo oxidation.
* Low energy HOMOs but large magnitude HOMO coefficients.

Borderline bases Aniline, pyridine, N3-, Br-, NO2-, SO32-, N2

 APPLICATIONS OF HSAB PRINCIPLE

There are numerous applications of the HSAB principle. It helps in understanding organic reaction
mechanisms, metal-ligand interactions in metal complexes, ore processing in metallurgy,
precipitations in qualitative analysis etc.

In hydrogen bonding:

The strong hydrogen bond is possible in cases of H2O, NH3, and HF,
since the donor atoms (F, O & N) are hard Lewis bases
and their interactions with partially positively charged H,
which is a hard acid, are stronger.
Linkage of ambidentate ligands to metal atoms:

It is one of the important applications of the HSAB principle.

The SCN- ligand is an ambidentate ligand and can be S-bound to metal (M-SCN) and referred to as
thiocyanate or can be N-bound to metal (M-NCS) and is referred to as isothiocyanate.

The choice among S-bound or N-bound is decided by soft or hard acid-base behavior.
S is a comparatively soft base than N atom.
Hence soft metal ions are S-bound while hard metal ions are N-bound.

1) SCN- bonds through sulfur atom (soft base) when bonded to Pt2+, a soft acid.

2) It bonds through nitrogen atom (a hard base) when linked to Cr 3+, a hard acid.

3) When Fe2+ reacts with SCN- a bright red [Fe(SCN)]+ ion is formed, whereas Cr3+ forms [Cr(NCS)]2+.
Reason: Fe2+ is a borderline acid and is S-bound. Whereas Cr3+ is hard acid and prefers to be N-
bound.

4) The molecule (CH3)2NCH2PF2 would bond to BF3 through N whereas it would bond to BH3 through P.
Reason: BF3 is a hard acid and prefers to bind with N atom - a hard base.
Whereas BH3 is a soft acid and preferentially bonded to soft base, P atom.
Symbiotic effect:

The hard-soft character of the metal ion is altered by the other groups attached.
It is referred to as a symbiotic effect.

For example, the isolated Co3+ is a hard acid and is expected to make the bond with SCN- ion
through N atom as observed in [Co(NH3)5(NCS)]3-.

However, when bound to five soft base ligands like CN - ions, the hardness of cobalt ion (Co3+)
is reduced.

Thus, [Co(CN)5]2- behaves as a soft acid and prefers to bind with SCN- ion through S atom to
form [Co(CN)5(SCN)]3-.
Application of HSAB to predict the direction of Inorganic reactions:

HSAB principle is used to predict the outcome of few of the reactions.

We can predict whether a reaction proceeds to the right or left based on soft or hard acid/base interactions.

1) The reaction between AsF3 and PI3 is possible and proceeds to the right since As3+ is softer than P3+ and I- is softer than F-.

More softer As prefers softer iodide over fluoride

Remember that both As3+ and P3+ are soft but relatively As3+ is softer due to larger size.

2) The reaction between MgS and BaO as shown below is possible

since Mg2+ is harder acid than Ba2+ and O2- is harder base than S2-.

harder acid Mg2+ combines with harder oxide ion

3) P2F4 can be prepared by treating PF2I with mercury as shown below.

2 PF2I + 2 Hg ------> Hg2I2 + P2F4

In this reaction, it is iodine rather than fluorine that is removed from PF2I.

Explanation: Hg22+ ion is a soft acid that prefers soft base I- rather than hard base F-.
Solubility in water:

The compound formed due to soft acid-soft base combination is more covalent and
less soluble in polar solvents like water.

For example, Silver iodide, AgI is insoluble in water as it has covalent nature since it
is the combination of soft acid, Ag+ and soft base, I-.

On the other hand, Lithium iodide, LiI is the result of a combination of Li+ (hard acid)
and I- (soft base).
Thus, it is polar covalent and thus soluble in water.
Hard Soft interactions - Types of ores:

We know that the hard metals prefer to bind with hard anions and thus they are
available as oxides or fluorides or carbonates or silicates in nature.
Whereas, the soft metals prefer to bind with soft anions and hence are found in
nature as sulfides or phosphides or selenides.

E.g. Aluminium is mostly found in nature as alumina, Al 2O3 - an oxide ore,

since Al3+ is a hard metal which prefers to combine with hard oxide anion rather
than the soft sulfide ion.

Silver & copper metals exist as sulfide ores since both Ag + and Cu2+ are soft metals.

The f-block elements are found in nature as silicate minerals since the trivalent
lanthanides are actinides are hard acids and tend to bind with hard oxygen bases as
in silicates.
Precipitation reactions & Qualitative analysis:
The softer acids like Ag+, Hg+, Hg2+ etc., and borderline acids like Fe2+ , Ni2+ , Cu2+ , Zn2+ , Pb2+ etc.,
can be precipitated as sulfides from their aqueous solutions since S2- ion is a softer base.
Following table illustrates the separation of cations based on their hardness or softness.

HSAB and Qualitative Analysis

Separation
Table
Group-1 Group-2 Group-3 Group-4 Group-5
Borderline &
HSAB acid Soft Borderline Hard Hard
soft
HCl H2S (acidic) H2S (basic) (NH4)2CO3 Soluble
Precipitates AgCl HgS MnS CaCO3
PbCl2 CdS FeS SrCO3 K+
Reagent Hg2Cl2 CuS CoS BaCO3 NH4+
SnS NiS
As2S3 ZnS
Sb2S3 Al(OH)3
Bi S Cr(OH)
Site preference:

1) RCOX is a hard acid and reacts with the nitrogen end of SCN- ion to form an acyl
isothiocyanate.

2) Whereas the softer methyl group bonds to the Sulfur atom and forms methyl thiocyanate.
methyl as soft acid + soft basic sulfur end

Nucleophilic addition of α,β-unsaturated carbonyl compounds:

The α,β-unsaturated carbonyl compounds have two types of carbon electrophilic centers.

1) Carbonyl carbon - Hard electrophilic center.

2) β-carbon - Soft electrophilic center.

Therefore, the hard nucleophiles like Grignard reagents attack the carbonyl carbon (hard
electrophile) resulting in 1,2-nucleophilic addition to C=O group.

E.g.,

Whereas, the soft nucleophiles like Lithium organocuprates, thiols etc. attack the β-carbon
(soft nucleophile) resulting in 1,4-conjugate addition.
 LIMITATIONS (DRAW BACKS) OF PEARSON'S HSAB MODEL

Pearson's HSAB theory is in direct contradiction with Fajan's rules.

For example, the later predict the nature of Beryllium salts to be more
covalent.
But according to the HSAB principle, the Be2+ ion is hard acid and is
expected to show charge controlled bonding that results in more ionic
nature for beryllium compounds.

But this is not true.

Since hydrogen ion, H+ is a hard acid and hydride ion, H- is a soft base,
according to HSAB principle the interactions between them must be polar
covalent and H2 must be unstable.

Indeed, H2 is a stable molecule with pure covalent nature.

 HSAB PRINCIPLE - MCQ - SOLVED QUESTIONS &
ANSWERS - CSIR NET GATE SET IIT JAM

Question-1: Which of the following is a borderline acid ?

A) Fe2+
B) Cu2+
C) Zn2+
D) All
Answer: D

Question-2: Which of the following is a soft acid ?

A) Ag+
B) Pt2+
C) Au+
D) All
Answer: D
Question-3: Which of the following is not a hard acid ?
A) H+
B) Li+
C) BH3
D) BF3
Answer: C

Question-4: Which of the following will combine with

BH3 to form a stable complex?
A) CO
B) Pt2+
C) OH-
D) methane
Answer: A
FONTE:

http://www.adichemistry.com/inorganic/cochem/hsab/hard-soft-acid-
base-theory.html
PEARSON CONCEPT: The HSAB concept

HSAB is the acronym for hard and soft acids and bases.

In 1958 Ahrland classified metal cations as Type A and Type B, where:

Type A metal cations included:

Alkali metal cations: Li+ to Cs+,
Alkaline earth metal cations: Be2+ to Ba2+
Lighter transition metal cations in higher oxidation states: Ti4+, Cr3+, Fe3+, Co3+,
The proton, H+

Type B metal cations include:

Heavier transition metal cations in lower oxidation states: Cu+, Ag+, Cd2+, Hg+,
Ni2+, Pd2+, Pt2+
In 1960, Ralph Pearson developed the Type A and Type B and classified Lewis acids
and Lewis bases as hard, borderline or soft.

Hard acid: A Lewis acid with an acceptor centre of low polarizability,

high positive charge, small size.

Soft Acids: A Lewis acid with an acceptor centre of high polarizability,

low positive charge, large size.

Hard Bases: A Lewis base with a donor centre of low polarizability,

high electron negativity, small size, no low energy empty d-orbitals.

Soft base: A Lewis base with a donor centre of high polarizability,

low electron negativity, large size, low energy empty d orbitals

HSAB principle:
Hard (Lewis) acids prefer to bind to hard (Lewis)
Bases Soft (Lewis) acids prefer to bind to soft (Lewis) bases
Example

Hard acid Al3+, the binding strength increases as the electrostatic parameter, ξ = z 2 / r

Soft acid Hg2+, the binding strength increases with increasing polarizability of the anion.
--------------------------------------------------------------------------------------------------------------------------

Chemical consequences of hardness

The tendency of soft acids to bond to soft bases and of hard acids to bond to hard bases
explains certain aspects of the Goldschmidt classification of the elements into 4 type.
(2 of the classes are the lithophile elements and the chalcophile elements.)

lithophile elements: Li, Mg, Ti, Al, Cr

(hard cations which are found in association to the hard base O2-)

chalcophile elements: Cd, Pb, Bi, Ag

(soft cations, which are found in associaion with the soft bases S2-, Se2-)
Teoria HSAB (WIKIPÉDIA)
A teoria HSAB, antes conhecida como "conceito HSAB", acrônimo do inglês hard and soft acid and bases ("ácidos
e bases duros e moles"), proposta por Ralph G. Pearson em 1963, amplamente usada em química para explicar a
estabilidade dos compostos químicos, reações químicas, etc.
Seu intento é classificar como "duro" ou "mole", "ácido" ou "base" as diversas espécies químicas envolvidas num
equilíbrio.

É uma extensão da teoria de Lewis. Ela prevê que reações ácido-base do tipo:

A +:B ⇄ A:B

na realidade, explica Pearson, as reações ocorrem totalmente (ou quase) no solvente. Desta ideia, parte para
tornar todas as reações ácido-base, em substituições do tipo:

A:B'+ A':B ⇄ A:B + A':B'

Um exemplo
Íons da terra rara Ln3+ são ácidos duros, com uma destacada afinidade para bases duras que ligam-se
através do oxigênio.
A água responde perfeitamente ao requisito e isto decorre da difícil reatividade em solução aquosa
destes íons.
Definição

Se aplica o termo duro, às espécies naturalmente pequenos,

com estados de elevada carga e dificilmente polarizáveis.

Mole diz-se daquelas espécies químicas que são naturalmente grandes,

possuem estados de baixa carga e são facilmente polarizáveis.

Ácidos duros: H+, íons alcalinos (por ex. Na+), Ti4+, Cr3+, Cr6+, BF3, íons Ln3+ …

Ácidos moles: CH3Hg+, Pd2+, Ag+, Hg2+, Hg22+, Cd2+, BH3, …

Bases duras: OH –, F –, (Cl – ), NH3, CH3COO –, CO32- …

Bases moles: R3P, S2–, I– ...

Em reações ácido-base de Lewis as ligações formadas são mais fortes na
reação de um ácido e uma base de carácter "duro-duro" e de caráter
"mole-mole".

Do ponto de vista da estrutura eletrônica, a característica de "dureza" e

de "moleza" é vinculada respectivamente à maior e menor diferença de
energia existente entre orbitais de fronteira.

Disto explica-se até a diferente polarização e o comportamento dos

campos perturbados externos, fator importante para a interpretação
mecânico quântico das ligações químicas.
Uma pequena (aparente) contradição:

O íon Fe3+ é um dos ácidos muito duro, enquanto o cianeto (CN-) é

uma base mole.
Com base na primeira formulação da teoria, a ligação seria então lábil
de ser quebrada em solução aquosa.
De fato, não se considerava o mecanismo retroligação π, na qual o
ferro funciona como base e o cianeto como ácido.

Este último tem efeitos orbitais de antiligação liberando onde dispôr

os elétrons cedidos do ferro;
uma vez formado o complexo, a ordenação da ligação do cianeto
passa de 3 (C≡N) para 2 (C=N).