HSAB theory

The HSAB concept is an acronym for 'hard and soft compounds, reaction mechanisms and pathways. It assigns the terms 'hard' or 'soft', and 'acid' or 'base' to chemical species. 'Hard' applies to species which are small, have high charge states (the charge criterion applies mainly to acids, to a lesser extent to bases), and are weakly polarizable. 'Soft' applies to species which are big, have low charge states and are strongly polarizable.^[1]

The theory is used in contexts where a qualitative, rather than quantitative description would help in understanding the predominant factors which drive chemical properties and reactions. This is especially so in ligands and transition metal ions in terms of their hardness and softness.

HSAB theory is also useful in predicting the products of metathesis reactions. Quite recently it has been shown that even the sensitivity and performance of explosive materials can be explained on basis of HSAB theory ^[2]

Ralph Pearson introduced the HSAB principle in the early 1960s^[3]^[4] as an attempt to unify inorganic and organic reaction chemistry.^[5].

Theory

The gist of this theory is that soft acids react faster and form stronger bonds with soft bases, whereas hard acids react faster and form stronger bonds with hard bases, all other factors being equal.^[6] The classification in the original work was mostly based on equilibrium constants for reaction of two Lewis bases competing for a Lewis acid.

Hard acids and hard bases tend to have:

small size
high oxidation state
low polarizability
high electronegativity
energy low-lying LUMO (acids).^[6]

Examples of hard acids are: H⁺, ionic in nature.

Soft acids and soft bases tend to have:

large size
low or zero oxidation state
high polarizability
low electronegativity
energy high-lying HOMO (bases) and energy-low lying LUMO (acids).^[6]

Examples of soft acids are: CH₃Hg⁺, Pt⁴⁺, Pd²⁺, Ag⁺, Au⁺, Hg²⁺, Hg₂²⁺, Cd²⁺, BH₃. Examples of soft bases are: H^–, R₃P, SCN^–, I^–. The affinity of soft acids and bases for each other is mainly covalent in nature.

Acids				Bases
hard		soft		hard	soft
Hydride	H^-
Thiolate	RS^-
Halogens	I^-
Phosphine	PR₃
Thiocyanate	SCN^-
carbon monoxide	CO
		bulk Benzene	C₆H₆
		Gold	Au⁺
Table 1. Hard and soft acids and bases

Borderline cases are also identified: borderline acids are trimethylborane, nitrate and sulphate anions.

Generally speaking, acids and bases interact and the most stable interactions are hard-hard (covalent character).

An attempt to quantify the 'softness' of a base consists in determining the equilibrium constant for the following equilibrium:

BH + CH₃Hg⁺ ↔ H⁺ + CH₃HgB

Where CH₃Hg⁺ (methylmercury ion) is a very soft acid and H⁺ (proton) is a hard acid, which compete for B (the base to be classified).

Some examples illustrating the effectiveness of the theory:

Bulk metals are soft acids and are poisoned by soft bases such as phosphines and sulfides.
Hard acetone are soft solvents with a preference for solvatating large anions and soft bases.
In coordination chemistry soft-soft and hard-hard interactions exist between ligands and metal centers.

Chemical hardness

Chemical hardness
Acids			Bases
Fluoride	F^-	7
Aluminum	Al³⁺	45.8	Ammonia	NH₃	6.8
hydride	H^-	6.8
carbon monoxide	CO	6.0
Sodium	Na⁺	21.1	hydroxyl	OH^-	5.6
cyanide	CN^-	5.3
phosphane	PH₃	5.0
nitrite	NO₂^-	4.5
Sulfur dioxide	SO₂	5.6	Hydrosulfide	SH^-	4.1
Iodine	I₂	3.4	Methane	CH₃^-	4.0
Table 2. Chemical hardness data

In 1983 Pearson together with Robert Parr extended the qualitative HSAB theory with quantitative chemical hardness (η) defined as ^[7]:

$\eta = 0.5(I - A) \,$

with $I\,$ the electron affinity.

When the Mulliken scale:

$\chi = 0.5(I + A) \,$

is the first derivative in a plot of energy $E\,$ versus the amount of nuclear charge $Z\,$ in an atom or molecule:

$\chi = \left(\frac{\partial E}{\partial N}\right)_Z \,$

then the chemical hardness is simply the second derivative:

$\eta = 0.5\left(\frac{\partial^2 E}{\partial N^2}\right)_Z \,$

Hardness and electronegativity are related as:

$2\eta = -\left(\frac{\partial \chi}{\partial N}\right)_Z \,$

and in this sense hardness is a measure for resistance to deformation or change. Likewise a value of zero denotes maximum softness.

In a compilation of hardness values only that of the Tl³⁺ compared to Tl⁺.

Kornblum's rule

An application of HSAB theory is the so-called Kornblum's rule which states that in reactions with ambident nucleophiles, the more carbocation (a hard acid) reacts with a hard base (high electronegativity) and that in a S_N2 reaction tetravalent carbon (a soft acid) reacts with ditto soft bases.

References

^ Jolly, W. L.. Modern Inorganic Chemistry. ISBN 0070327602.
^ [1]E.-C. Koch, Acid-Base Interactions in Energetic Materials: I. The Hard and Soft Acids and Bases (HSAB) Principle-Insights to Reactivity and Sensitivity of Energetic Materials, Prop.,Expl.,Pyrotech. 30 2005, 5
^ Pearson, Ralph G. (1963). "Hard and Soft Acids and Bases". J. Am. Chem. Soc. 85 (22): 3533 - 3539. doi:10.1021/ja00905a001.
^ Pearson, Ralph G.. "Hard and soft acids and bases, HSAB" (subscriber access). J. Chem. Educ. 1968 (45): 581643.
^ [2]R. G. Pearson, Chemical Hardness - Applications From Molecules to Solids, Wiley-VCH, Weinheim, 1997, 198 pp
^ ^a ^b ^c IUPAC, Glossary of terms used in theoretical organic chemistry, accessed 16 Dec 2006.
^ Robert G. Parr and Ralph G. Pearson (1983). "Absolute hardness: companion parameter to absolute electronegativity". J. Am. Chem. Soc. 105 (26): 7512 - 7516. doi:10.1021/ja00364a005.
^ The Mechanism of the Reaction of Silver Nitrite with Alkyl Halides. The Contrasting Reactions of Silver and Alkali Metal Salts with Alkyl Halides. The Alkylation of Ambident Anions Nathan Kornblum, Robert A. Smiley, Robert K. Blackwood, Don C. Iffland J. Am. Chem. Soc.; 1955; 77(23); 6269-6280. doi:10.1021/ja01628a064

HSAB theory

Theory

Chemical hardness

Kornblum's rule

References

See also