Electron pair, Lewis acid-base definition

A Lewis acid is any species capable of accepting a pair of electrons, and a Lewis base is a species with a pair of electrons available for donation. The terms acceptor and donor are also commonly used. Lewis acids include H+ and metal cations, molecules such as BF3 with incomplete octets, and ones such as SiF4 where octet expansion is possible (see Topic Cl). Any species with nonbonding electrons is potentially a Lewis base, including molecules such as NH3 and anions such as F. The Lewis acid-base definition should not be confused with the Bronsted one (see Topic E2) Bronsted bases are also Lewis bases, and H+ is a Lewis acid, but Bronsted acids such as HC1 are not Lewis acids. 

The American chemist G. N. Lewis formulated such a definition. He defined what we now call a Lewis base as a substance that can donate a pair of electrons. A. Lewis acid is a substance that can accept a pair of electrons. For example, in the protonation of ammonia, NH3 acts as a Lewis base because it donates a pair of electrons to the proton H, which acts as a Lewis acid by accepting the pair of electrons. A Lewis acid-base reaction, therefore, is one that involves the donation of a pair of electrons from one species to another. Such a reaction does not produce a salt and water. 

In the Lewis acid-base definition, an acid is any species that accepts a lone pair to form a new bond in an adduct. Thus, there are many more Lewis acids than other types. Lewis adds include molecules with electron-deficient atoms, molecules with polar multiple bonds, and metal cations. 

Electron-Pair Donation and the Lewis Acid-Base Definition... 

By focusing on where the proton comes from and goes to, the Brpnsted-Lowry concept expands the definition of a base to encompass a host of species that the Arrhenius definition excludes a base is any species that accepts a proton to do so, the base must have a lone electron pair. (The lone electron pair also plays the central role in the Lewis acid-base definition, as you ll see later in this chapter.)... 

ELECTRON-PAIR DONATION AND THE LEWIS ACID-BASE DEFINITION... 

The final acid-base concept we consider was developed by Gilbert N. Lewis, whose contribution to understanding the importance of valence electron pairs in molecular bonding we discussed in Chapter 9. Whereas the Brpnsted-Lowry concept focuses on the proton in defining a species as an acid or a base, the Lewis concept highlights the role of the electron pair. The Lewis acid-base definition holds that... 

The Lewis acid-base definition focuses on the donation or acceptance of an electron pair to form a new covalent bond in an adduct, the product of an acid-base reaction. Lewis bases donate the electron pair, and Lewis acids accept it. Thus, many species that do not contain El are Lewis acids. Molecules with polar double bonds act as Lewis acids, as do those with electron-deficient atoms. Metal ions act as Lewis acids when they dissolve in water, which acts as a Lewis base, to form an adduct, a hydrated cation. Many metal ions function as Lewis acids in biomolecules. 

Lewis acid-base definition A model of acid-base behavior in which acids and bases are defined, respectively, as species that accept and donate an electron pair. (606)... 

According to the Lewis acid-base definition, an acid is an electron pair acceptor and a base is an electron pair donor. 

The Arrhenius and Bronsted-Lowry definitions describe most acids and bases. Both definitions assume that the acid contains or produces hydrogen ions. A third acid classification, based on bonding and structure, includes, as acids, substances that do not contain hydrogen at all. This definition of acids was introduced in 1923 by G. N. Lewis, the American chemist whose name was given to electron-dot structures. Lewis s definition emphasizes the role of electron pairs in acid-base reactions. 

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. 

Since Arrhenius, definitions have extended the scope of what we mean by acids and bases. These theories include the proton transfer definition of Bronsted-Lowry (Bronsted, 1923 Lowry, 1923a,b), the solvent system concept (Day Selbin, 1969), the Lux-Flood theory for oxide melts, the electron pair donor and acceptor definition of Lewis (1923, 1938) and the broad theory of Usanovich (1939). These theories are described in more detail below. 

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. 

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... 

Although many other acid-base definitions have been proposed and have been useful in particular types of reactions, only a few have been widely adopted for general use. Among them are those attributed to Arrhenius (based on hydrogen and hydroxide ion formation), Br0nsted-Lowry (hydrogen ion donors and acceptors), and Lewis (electron pair donors and acceptors) [6,67-70]. 

All Br0nsted-Lowry acids are Lewis acids, but in practice, the term Lewis acid is generally reserved for Lewis acids that don t also fit the Bronsted-Lowry definition. The best way to spot a Lewis acid-base pair is to draw a Lewis dot structure of the reacting substances, noting the presence of lone pairs of electrons. (We introduce Lewis structures in Chapter 5.) For example, consider the reaction between ammonia (NH3) and boron trifluoride (BFj) ... 

Reaction 3.2 is a prime example of the use of the terms Lewis acid and Lewis base. G. N. Lewis suggested the usage such that a donor of an electron pair is a base and the acceptor molecule is an acid. The classical Bransted acid and base pair, H+(aqueous) and OH (aqueous), are encompassed by the Lewis definitions as they combine to give water, the hydroxide ion supplying both electrons. 

Thus, by definition, electrophiles are electron-pair acceptors and nucleophiles are electron-pair donors. These definitions correspond closely to definitions used in the generalized theory of acids and bases proposed by G. N. Lewis (1923). According to Lewis, an acid is any substance that can accept an electron pair, and a base is any substance that can donate an electron pair to form a covalent bond. Therefore acids must be electrophiles and bases must be nucleophiles. For example, the methyl cation may be regarded as a Lewis acid, or an electrophile, because it accepts electrons from reagents such as chloride ion or methanol. In turn, because chloride ion and methanol donate electrons to the methyl cation they are classified as Lewis bases, or nucleophiles ... 

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