Acids Lewis concept

R. G. Pearson, J. Am. Chem. Soc. 85 3533 (1963) T. L. Ho, Hard and Soft Acids and Bases in Organic Chemistry, Academic Press, New York, 1977 W. B. Jensen, The Lewis Acid-Base Concept, Wiley-Interscience, New York, 1980, Chapter 8. 

The strength of the complexation is a function of both the donor atom and the metal ion. The solvent medium is also an important factor because solvent molecules that are potential electron donors can compete for the Lewis acid. Qualitative predictions about the strength of donor-acceptor complexation can be made on the basis of the hard-soft-acid-base concept (see Section 1.2.3). The better matched the donor and acceptor, the stronger is the complexation. Scheme 4.3 gives an ordering of hardness and softness for some neutral and ionic Lewis acids and bases. 

For a monograph on Lewis acid-base theory, see Jensen, W.B. The Lewis Acid-Base Concept Wiley NY, 1980. For a discussion of the definitions of Lewis acid and base, see Jensen, W.B. Chem. Rev, 1978, 78, 1. 

W. B. Jensen, The Lewis Acid-Base Concepts, An Overview, John Wiley Sons, Hoboken, NJ, 1980. 

C21-0089. The fluorides BF3, AIF3, SiFq, and PF5 are Lewis acids. They all form very stable fluoroanions when treated with lithium fluoride. In contrast, three other fluorides, CF4, NF3, and SFg, do not react with lithium fluoride. Use Lewis acid-base concepts to explain this behavior. 

Cations at the surface possess Lewis acidity, i.e. they behave as electron acceptors. The oxygen ions behave as proton acceptors and are thus Bronsted bases. This has consequences for adsorption, as we will see. According to Bronsted s concept of basicity, species capable of accepting a proton are called a base, while a Bronsted acid is a proton donor. In Lewis concept, every species that can accept an electron is an acid, while electron donors, such as molecules possessing electron lone pairs, are bases. Hence a Lewis base is in practice equivalent to a Bronsted base. However, the concepts of acidity are markedly different. 

The Lewis concept permits inclusion of acids and oxidants in a single... 

Resonance such as (5.28a)-(5.28c) is inherently a quantal phenomenon, with no classical counterpart. In NBO language, each of the resonance interactions (5.28a)-(5.28c) corresponds to a donor-acceptor interaction between a nominally filled (donor Lewis-type) and unfilled (acceptor non-Lewis-type) orbital, the orbital counterpart of G. N. Lewis s general acid-base concept. As mentioned above, Lewis and Werner (among others) had well recognized the presence of such valence-like forces in the dative or coordinative binding of free molecular species. Thus, the advent of quantum mechanics and Pauling s resonance theory served to secure and justify chemical concepts that had previously been established on the basis of compelling chemical evidence. 

Usanovich (1934) modified the Lewis concept of acid and base by removing the restriction of either donation or acceptance of the electron pair in a more generalized fashion. According to him ... 

It should be kept in mind that the terms acidity and basicity of the solvent have to be intended not only according to the Lewis concept (electrophilic vs. nucleophilic properties), but also according to the Bronsted concept (proton donor vs. proton acceptors), or to the hydrogen bonding capacity (hydrogen bond donor vs. hydrogen bond acceptor). 

I. Definition of Basicity A. General Comments on the Acid-base Concept The current general definition of the acid-base concept is based on the definitions by Bronsted and Lewis. According to Bronsted s theory (1923) an acid-base interaction can be described by the general relation (1) ... 

These and similar solvents are distinguished by the fact that they themselves cannot eliminate any protons. On the other hand one is still dealing with water-like solvents in the case of alcohols, since the selfdissociation of the alcohols resembles that of water in order of magnitude (see Gurney, 1953). The ability of free electron pairs to function prompted Lewis (1923) to a more general definition of the acid-base concept. 

Jensen WB (1980) The Lewis acid-base concept. Wiley, New York... 

According to the acid-base concept of Pearson, A -phosphorins can be viewed as soft bases the lone electron pair at phosphoms is much more delocalized than the lone pair at nitrogen in pyridine. Thus, such soft Lewis acids as Hg ions are more likely to react with A -phosphorins (see p. 84). 

A Lewis acid (electrophile) shares an electron pair furnished by a Lewis base (nucleophile) to form a covalent (coordinate) bond. The Lewis concept is especially useful in explaining the acidity of an aprotic acid (no available proton), such as BFj. 

An example of the different points of view and different tastes in the matter of acid-base definitions was provided to one of the authors in graduate school while attending lectures on acid-base chemistry from two professors. One Felt that the solvent system was very useful, but that the Lewis concept went too far because it included coordination chemistry. The second used Lewis concepts in all of his work, but felt uncomfortable with the Usanovich definition because it included redox chemistry To the latter s credit, however, he realized that the separation was an artificial one, and he suggested the pyridine oxide example given above. 

The Lewis definition thus encompasses all reactions entailing hydrogen ion. oxide ion. or solvent interactions, as well as the formation of acid-base adducts such as R,NBF, and all coordination compounds. Usage of the Lewis concept is extensive in both inorganic and organic chemistry, and so no further examples will be given here, but many will be encountered throughout the remainder of the book.11... 

NUCLEOPHILE. An ion or molecule that donates a pair of electrons to an atomic nucleus to form a covalent bond. The nucTeus that accepts the electrons is called an electrophile. This occurs, for example, in the formation of acids and bases according to the Lewis concept, as well as in covalent bonding in organic compounds. 

The generalized Lewis concept of acids and bases also includes common proton-transfer reactions.1 Thus water acts as a base because one of the... 

G.N. Lewis extended and generalized the acid-base concept to nonprotonic systems.5,6 He defined an acid as a substance that can accept electrons and defined a base as a substance that can donate electrons. Lewis acids are electron-deficient molecules or ions such as BF3 or carbocations, whereas Lewis bases are molecules that contain readily available nonbonded electron pairs (as in ethers, amines, etc.) [Eq. (1.6)]. 

Even more general is the Lewis concept of acids and bases a Lewis base has a lone pair available for formation of a coordinate bond, and a Lewis acid has a vacant acceptor orbital handy. This concept is applicable to reactions in the gas phase or in inert solvents (as discussed in the previous section) as well as to complex formation in solution and the acid/ base phenomena studied by Arrhenius, Br0nsted and Lowry. 

Lewis has defined acids and bases in a general way as electron acceptors and donors, respectively (21). Accordingly, a compound or element capable of accepting electrons (electron seeking) is termed a Lewis acid. Conversely a compound or element capable of giving (or sharing electrons) is a Lewis base. In other words, those elements which are deficient in electrons --that is, have unfilled electron shells -- will seek out those elements carrying extra electrons (lone pairs). This is the basis for the Lewis concept of "acid -base interaction. Thus ... 

Empirically measured parameters are additional solvent properties, which have been developed through the efforts of physical chemists and physical organic chemists in somewhat different, but to some extent related, directions. They have been based largely on the Lewis acid base concept, which was defined by G. N. Lewis. The concept originally involved the theory of chemical bonding which stated that a chemical bond must involve a shared electron pair. Thus, an atom in a molecule or ion which had an incomplete octet in the early theory, or a vacant orbital in quantum mechanical terms, would act as an electron pair acceptor (an acid) from an atom in a molecule or ion which had a complete octet or a lone pair of electrons (a base). Further developments have included the concepts of partial electron transfer and a continuum of bonding from the purely electrostatic bonds of ion-ion interactions to the purely covalent bonds of atoms and molecules. The development of the concept has been extensively described (see Ref. 11 for details). 

The Lewis concept of the acid is included in the AP curriculum but is not emphasized as much as the other two descriptions. As a result, we will just look at the main ideas. 

The Lewis concept deals with the behavior of electron pairs in chemical reactions. The same electron pairs we looked at when we discussed molecular geometry (see Chapter 7) can be involved in many reactions. Substances that can form a covalent bond by accepting an electron pair from another substance are known as Lewis acids. Substances that can form a covalent bond by donating an electron pair to another substance are known as Lewis bases. Be careful that you don t mix these up with the Bronsted-Lowry acids and bases. It is easy to do since the words donate and accept are used, except they are associated with the opposite species (Bronsted-Lowry acids donate protons, while Lewis acids accept electron pairs). 

---