Lewis acid definition

We have seen that a base can be defined as combining with a proton and, therefore, requires at least one lone pair of electrons. A more general definition of acids and bases, due to G. N. Lewis, describes a base as any species (atom, ion or molecule) which can donate an electron pair, and an acid as any species which can accept an electron pair— more simply, a base is an electron-pair donor, an acid an electron-pair acceptor. Some examples of Lewis acids and bases are ... 

If we apply Lewis s definitions narrowly we can write an equation for the reac tion between a Lewis acid and a Lewis base as... 

The Lewis definitions of acids and bases provide for a more general view of acid-base reactions than either the Arrhenius or Br0nsted-Lowry pic ture A Lewis acid is an electron pair acceptor A Lewis base is an electron pair donor The Lewis approach incorporates the Br0nsted-Lowry approach as a subcategory m which the atom that accepts the electron pair m the Lewis acid is a proton... 

Super Lewis Acids. Acid systems stronger than anhydrous AlCl ate classified as super Lewis acids (211). By this definition, Lewis acids such as SbF, NbF, AsF, andTaF ate so categorized. 

For the sake of completeness, it is worthwhile to briefly discuss role of acid-base interactions in adhesion. In this context, the term acid refers to a Lewis acid (an electron acceptor) and a Lewis base (electron donor), rather than the more conventional acid and base definitions. The role of acid-base interactions in adhesion is discussed in detail by Lee [105]. 

The Lewis definition of acids and bases is broader and more encompassing than the Bronsted-Lowry definition because it s not limited to substances that donate or accept just protons. A Lewis acid is a substance that accepts an electron pair, and a Lewis base is a substance that donates an electron pair. The donated electron pair is shared between the acid and the base in a covalent bond. 

The fact that a Lewis acid is able to accept an electron pair means that it must have either a vacant, low-energy orbital or a polar bond to hydrogen so that it can donate H+ (which has an empty7 Is orbital). Thus, the Lewis definition of acidity includes many species in addition to H+. For example, various metal cations, such as Mg2+, are Lewis acids because they accept a pair of electrons when they form a bond to a base. We ll also see in later chapters that certain metabolic reactions begin with an acid-base reaction between Mg2+ as a Lewis acid and an organic diphosphate or triphosphate ion as the Lewis base. 

The Lewis definition of a base as a compound with a pair of nonbonding electrons that it can use to bond to a Lewis acid is similar to the Bronsted-Lowry definition. Thus, H20, with its two pairs of nonbonding electrons on oxygen, acts as a Lewis base by donating an electron pair to an H+ in forming the hydronium ion, H30+. 

If the definitions of nucleophiles and electrophiles sound similar to those given in Section 2.11 for Lewis acids and Lewis bases, that s because there is... 

A1C13, or S02 in an inert solvent cause colour changes in indicators similar to those produced by hydrochloric acid, and these changes are reversed by bases so that titrations can be carried out. Compounds of the type of BF3 are usually described as Lewis acids or electron acceptors. The Lewis bases (e.g. ammonia, pyridine) are virtually identical with the Bransted-Lowry bases. The great disadvantage of the Lewis definition of acids is that, unlike proton-transfer reactions, it is incapable of general quantitative treatment. 

This area of reactivity has been the subject of excellent reviews (J5). Silyl enol ethers are not sufficiently nucleophilic to react spontaneously with carbonyl compounds they do so under the influence of either Lewis acids or fluoride ion, as detailed above. Few clear trends have emerged from the somewhat limited number of definitive studies reported so far, with ambiguities in diastereoisomeric assignments occasionally complicating the issue even further. 

Many of the d-block elements form characteristically colored solutions in water. For example, although solid copper(II) chloride is brown and copper(II) bromide is black, their aqueous solutions are both light blue. The blue color is due to the hydrated copper(II) ions, [Cu(H20)fJ2+, that form when the solids dissolve. As the formula suggests, these hydrated ions have a specific composition they also have definite shapes and properties. They can be regarded as the outcome of a reaction in which the water molecules act as Lewis bases (electron pair donors, Section 10.2) and the Cu2+ ion acts as a Lewis acid (an electron pair acceptor). This type of Lewis acid-base reaction is characteristic of many cations of d-block elements. 

Lewis acidity. A 77-acid is a ligand that can accept electrons hv using 17-orbitals, and a 17-base donates electrons by using 17-orbitals. On the basis of these definitions, describe each of the following ligands as either a ir-acid, a ir-base, or neither ... 

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. 

Although Lewis and Bronsted bases comprise the same species, the same is not true of their acids. Lewis acids include bare metal cations, while Bronsted-Lowry acids do not. Also, Bell (1973) and Day Selbin (1969) have pointed out that Bronsted or protonic acids fit awkwardly into the Lewis definition. Protonic acids cannot accept an electron pair as is required in the Lewis definition, and a typical Lewis protonic add appears to be an adduct between a base and the add (Luder, 1940 Kolthoff, 1944). Thus, a protonic acid can only be regarded as a Lewis add in the sense that its reaction with a base involves the transient formation of an unstable hydrogen bond adduct. For this reason, advocates of the Lewis theory have sometimes termed protonic adds secondary acids (Bell, 1973). This is an unfortunate term for the traditional adds. 

Jensen, W. B. (1978). The Lewis acid-base definitions a status report. Chemical Reviews, 78, 1-22. 

It was G. N. Lewis who extended the definitions of acids and bases still further, the underlying concept being derived from the electronic theory of valence. It provided a much broader definition of acids and bases than that provided by the Lowry-Bronsted concept, as it furnished explanations not in terms of ionic reactions but in terms of bond formation. According to this theory, an acid is any species that is capable of accepting a pair of electrons to establish a coordinate bond, whilst a base is any species capable of donating a pair of electrons to form such a coordinate bond. A Lewis acid is an electron pair acceptor, while a Lewis base is an electron pair donor. These definitions of acids and bases fit the Lowry-Bronsted and Arrhenius theories, and cover many other substances which could not be classified as acids or bases in terms of proton transfer. 

According to Lewis s definition of an acid, that means that DNA is capable of accepting electrons. Unfortunately for the human body, DNA often accepts electrons from oxygen. Certainly the human body needs oxygen to live, but, under certain circumstances, oxygen can also have a harmful effect on the body. 

Upon dimerization, electron charge is transferred from the base (the H-acceptor molecule) to the acid (the H-donor molecule), in agreement with Lewis generalized definition of an acid and a base as an electron acceptor and donor, respectively. The amount of such a charge transfer (CT) is reported in Table 4, for the two SCF models considered in this paper and as a function of the basis set size. The CTs are small and, for the SCF-SM method, are found to decrease as the basis set size increases. 

The Lewis acids that also fulfil the Br0nsted definition form a special group of protonic acids and can be formally considered to be the products of neutralization of a proton by a base (for example Cl"). 

Before studying some examples more closely, let us consider some cases which are not listed in Table 13. There are numerous compounds SnX2 which are definitely monomeric but are nevertheless no carbene analogs since their valence electron number at the tin atom is at least eight. These compounds contain chelating ligands which can stabilize the carbenoid tin atom due to intramolecular Lewis acid-base interactions as shown by structure A and B (see also Chapter 3). 

An impressive combination of two Diels-Alder reactions is also described by Winkler [4] for the synthesis of the taxane skeleton, though two different Lewis acids must be used for the two cycloadditions. Thus, it does not strictly match the definition of a domino reaction. 

B The Lewis Definition of Acids and Bases 1. Lewis acid-base theory in 1923 proposed by G. N. Lewis (1875-1946 Ph. D. Harvard, 1899 professor, Massachusetts Institute of Technology, 1905-1912 professor, University of California, Berkeley, 1912-1946). 

Perhaps the greatest area in which the Lewis acid-base approach is most useful is that of coordination chemistry. In the formation of coordination compounds, Lewis acids such as Cr3+, Co3+, Pt2+, or Ag+ bind to a certain number (usually 2, 4, or 6) of groups as a result of electron pair donation and acceptance. Typical electron pair donors include H20, NH3, F , CN , and many other molecules and ions. The products, known as coordination compounds or coordination complexes, have definite structures that are predictable in terms of principles of bonding. Because of the importance of this area of inorganic chemistry, Chapters 16 through 22 in this book are devoted to coordination chemistry. 

An interesting pericyclic-anionic-pericyclic domino reaction showing a high stereoselectivity is the cycloaddition-aldol-retro-ene process depicted in scheme 20.1581 The procedure presumably starts with a [4+2]-cycloaddition of diene 98 and S02 in presence of a Lewis acid. After opening of the formed adduct reaction with (Z)-silyl vinyl ether 99 leads to a mixture of alk-2-enesulfinic acids 101. It follows a retro-ene reaction which affords a 7 3 mixture of the products 102 and 103. The reaction described by Vogel et al is a nice example for the efficient generation of polypropionate chains with the stereoselective formation of three stereogenic centers and one (0-double bond in a three-component domino reaction in its strict definition. 

In the same year, Lewis proposed an alternative definition According to Lewis, an acid is ary species that can accept a pair of electrons because of the presence of an incomplete electronic grouping. Hence, a Lewis base is any species that possesses a nonbonding electron pair that can the donated to form a coordination or dative bond. The Lewis acid-base interaction is given by... 

Thus, according to the above definitions, Lewis bases are also Bronsted bases but Lewis acids do not correspond to Bronsted acids. 

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