Acid-base Pearson hard-soft definition

In chemistry, the American chemist Ralph G. Pearson (1963) introduced the concept of hardness. Originally, the definition referred to hard and soft acids and bases. The hard-soft acid-base (HSAB) principle states that hard Lewis acids prefer hard Lewis bases and conversely that soft Lewis acids prefer soft Lewis bases. We will not dig deeply into the chemical background here. What is important is that Pearson (-1980) later found that hardness may simply be defined as... 

Just like Sanderson s electronegativity equalization principle, the Hard and Soft Acids and Bases principle was originally introduced without strong theoretical basis. Nevertheless, it was used widely from its formulation on. The principle states that hard acids prefer to coordinate with hard bases and soft acids with soft bases [82], In 1983, Parr and Pearson provided a definition for the chemical hardness [25]... 

However, in many cases, electronegativity difference alone cannot account for the stability of the molecule. For example, according to the electronegativity criterion, the CsF molecule should be very stable as the electronegativity difference between Cs and F is very large. But the reaction enthalpy data indicate that Fil and CsF will react to form Csl and FiF. In order to predict the direction of acid-base reactions and to account for the stability of the products, Pearson introduced two parameters hardness and softness in the vocabulary of chemistry. The qualitative definitions of hard and soft acids and bases are as follows [28-32] ... 

The FMO definition also helps explain why Pearson s hard-hard and soft-soft interactions form stable complexes. Hard compounds have a large HOMO-LUMO gap, as shown in Figure 14.9 for F. Therefore, hard Lewis acid-base complexes tend to form strongly ionic compounds, such as LiF, where the interaction is dominated by electrostatic attractions. Soft compounds, on the other hand, have a small HOMO-LUMO gap, as shown in Figure 14.9 for I, so that these types of interactions form covalently bonded acid-base adducts, where the strength of the interaction is controlled primarily by the energies of the FMOs that participate in the bonding. 

Particularly relevant to the present crmtext is the fact that the olefinic double bond is considered as a soft base in Pearson s theory, while many Lewis acids used in cationic polymerisation (BF3, BCI3, AICI3, etc.) are classed as hard acids. Obviously, n-acceptors like chloranil or tetracyanoethylene are considered as soft acids. Thus, the interactions between Lewis acids and olefins must be considered as very weak in the context of the HSAB theory. This prediction is well substantiated by the tenuous character of the complexes observed in experimental studies (see Chap. IV). On the other hand, carbenium ions are usually placed at the borderline between hard and soft acids and are definitely softer than the Lewis acids mentioned above. Consequently, their interactions with olefins must be rather strong, which suggests that that propagation in cationic polymerisations promoted by Lewis acids should be faster than initiation. 

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