Pearson hard-soft acid-base

Drago and co-workers Introduced an empirical correlation to calculate the enthalpy of adduct formation of Lewis acids and bases ( 5). In 1971, he and his co-workers expanded the concept to a computer-fitted set of parameters that accurately correlated over 200 enthalpies of adduct formation ( ). These parameters were then used to predict over 1200 enthalpies of interaction. The parameters E and C are loosely Interpreted to relate to the degree of electrostatic and covalent nature of the Interaction between the acids and bases. This model was used to generalize the observations involved in the Pearson hard-soft acid-base model and render it more quantitatively accurate. 

The important step involves the solubilization of inorganic compounds into the micellar core. As a guideline for optimum precursor materials and micellar core blocks, one can use Pearsons hard / soft acid /base (HSAB) concept [151], which has been generalized to include metals and semiconductors [152]. The general strategy is to start from weakly coordinated metals, e.g. Pd(OAc)2 or Pd(C104)2 which are complexes of a soft acid (the transition metal ions) and a hard base (acetates, perchlorates, etc.). The formation of more stable complex of a soft acid with a softer base, e.g. polyvinylpyridine, to assemble the micellar core, is the driving force for solubilization. The polymer complex should not be too stable since over-stabilization could prevent the formation of the desired colloid in the subsequent chemical reaction. 

Pearson, R. G. (1963). /. Am. Chem. Soc. 85, 3533. The original publication of the hard-soft acid-base approach by Pearson. 

Ayers, P. W., Parr, R. G., and Pearson, R. G. 2006. Elucidating the hard/soft acid/base principle A perspective based on half-reactions. J. Chem. Phys. 124 194107. 

Further examination of the results indicated that by invocation of Pearson s Hard-Soft Acid-Base (HSAB) theory (57), the results are consistent with experimental observation. According to Pearson s theory, which has been generalized to include nucleophiles (bases) and electrophiles (acids), interactions between hard reactants are proposed to be dependent on coulombic attraction. The combination of soft reactants, however, is thought to be due to overlap of the lowest unoccupied molecular orbital (LUMO) of the electrophile and the highest occupied molecular orbital (HOMO) of the nucleophile, the so-called frontier molecular orbitals. It was found that, compared to all other positions in the quinone methide, the alpha carbon had the greatest LUMO electron density. It appears, therefore, that the frontier molecular orbital interactions are overriding the unfavorable coulombic conditions. This interpretation also supports the preferential reaction of the sulfhydryl ion over the hydroxide ion in kraft pulping. In comparison to the hydroxide ion, the sulfhydryl is relatively soft, and in Pearson s theory, soft reactants will bond preferentially to soft reactants, while hard acids will favorably combine with hard bases. Since the alpha position is the softest in the entire molecule, as evidenced by the LUMO density, the softer sulfhydryl ion would be more likely to attack this position than the hydroxide. 

The utilization of Pearson s hard-soft acid-base theory to interpret the reactions of lignin has also been described in work from the Soviet Union by Zarubin and Kirysun (59). Beyond this specifically related paper, researchers in the Soviet Union have been quite active in the application of numerical methods to lignin-related problems (60,61). 

Hardness and softness as chemical concepts were presaged in the literature as early as 1952, in a paper by Mulliken [138], but did not become widely used till they were popularized by Pearson in 1963 [139]. In the simplest terms, the hardness of a species, atom, ion or molecule, is a qualitative indication of how polarizable it is, i.e. how much its electron cloud is distorted in an electric field. The adjectives hard and soft were said to have been suggested by D.H. Busch [140], but they appear in Mulliken s paper [138], p. 819, where they characterize the response to spatial separation of the energy of acid-base complexes. The analogy with the conventional use of these words to denote resistance to deformation by mechanical force is clear, and independent extension, by more than one chemist, to the concept of electronic resistance, is no surprise. The hard/soft concept proved useful, particularly in rationalizing acid-base chemistry [141]. Thus a proton, which cannot be distorted in an electric field since it has no electron cloud (we ignore the possibility of nuclear distortion) is a very hard acid, and tends to react with hard bases. Examples of soft bases are those in which sulfur electron pairs provide the basicity, since sulfur is a big fluffy atom, and such bases tend to react with soft acids. Perhaps because it was originally qualitative, the hard-soft acid-base (HSAB) idea met with skepticism from at least one quarter Dewar (of semiempirical fame) dismissed it as a mystical distinction between different kinds of acids and bases [142]. For a brief review of Pearson s contributions to the concept, which has been extended beyond strict conventional acid-base reactions, see [143],... 

Woerpel and Nevarez demonstrated the synthetic potential of silaaziridines by selective insertion reactions (Scheme 7.52).123 Silver-catalyzed aldehyde insertion into the Si-N bond of 169b produced the N,0-cyclic acetal 180 as the cis isomer. In contrast to this process, insertion of tert-butyl isocyanide occurred into the weaker C-Si bond to afford imine 181. The authors rationalized the chemoselectivity for these two processes on the basis of Pearson s hard-soft acid-base theory 124-126 the more ionic Si-N bond reacted with harder benzaldehyde electrophile, whereas the more covalent Si-C bond reacted with the softer isocyanide. 

A very important finding is that hard cations (e.g., Be2+, Al3+, Ti4+) prefer ligands with hard donor atoms (e.g., F, O, Cl), and soft cations (e.g., Ag+, Cd2+, Tl+) prefer ligands with soft donor atoms (e.g., I, Te, As). This fact has a myriad of applications, because it can be advantageously used for analysis, selective reactions, metal ion separation, removal, recovery, etc. It is an application of the Hard Soft Acid Base (HSAB) principle enunciated by Pearson at the end of the 1960s. 

Pearson s Hard-Soft-Acid-Base (HSAB) priciple is that hard add-base combinations form readily and are generally ionic compounds. The other group of stable compounds and complex ions involves the interaction between soft acid and soft bases. For these, the bonding is primarily covalent with interpenetrating orbitals. The combinations hard acid with soft base, or vice versa, have little stability. 

This mixed ligand coordination where carboxylate and pyridyl groups are bound to the same cation is not common. In fact, one could argue that this is in contrast to Pearson s hard/soft acid-base distinction in that the uranyl cation is a hard acid and the dipyridyl linkers are softer in nature. Indeed, U02 -pyridyl coordination (2,2 -bipyridine, terpyridines, etc) is quite rare, even in molecular materials, yet in these extended topologies, it is likely that sterics play a considerable role and that the 4,4 -dipyridyl is uniquely suited to displace H2O groups and serve as a bridging moiety. This is mentioned in this context as... 

Recently Parr and Pearson have used the b parameter to investigate the hard and soft properties of metal ions and ligands. They have termed this the absolute hardness in comparison to the Mulliken-Jaff6 a parameter which they call absolute electronegativity. They provide strong arguments for the use of the absolute hardness parameter in treating hard-soft acid-base (HSAB) interactions. 

Formation constants for many metal complexes have been compiled by Ramunas Motekaitis and Art Martell, and these as well as techniques for measuring them in the laboratory will be covered in Chapters 3 and 8. One can, however, predict the relative stability of a desired complex based on simple bonding theories. Crystal field theory, as well as the Irving-Williams series and Pearson s hard-soft-acid-base theory (see the next section) enable us to predict what might happen in solution. 

The qualitative concepts of hardness and softness were first introduced by Pearson [30-32,34], which later culminated in enunciation of the famous hard-soft acid-base principle. Quantification of these concepts had been in order and was accomplished within density functional theory by Parr and Pearson [52]. The energy stabilization due to soft-soft interaction can be expressed by rearranging Eq. (61) as [52] ... 

In terms of Pearson s hard-soft acid-base principle, the soft Lewis acid copper ion is not compatible with the hard base H20 molecule, but a recent article provided the first example of a copper(I)-water bond (240). The novel copper complex with 2,3-diphenylquinoxaline (L 1), [Cu(L91)(H20)]C104, is diamagnetic and indefinitely stable in air in the solid state. Its structure consists of an infinite polymeric cationic chain in which adjacent metal centers are bridged by the aro-... 

Finally, it must be mentioned that acid-base interactions can also be analyzed in terms of Pearson s hard-soft acid-base (HSAB) principle [56,57]. At present, the application of this concept to solid-solid interactions and thus to adhesion is under investigation. 

Pearson, R. G. (1972). [Quantitative evaluation of the HSAB (hard-soft acid-base) concept]. Reply to the paper by Drago and Kabler (1972). Inorg. Chem. 11, 3146. 

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