Electrophile-nucleophile acid-base definition

The Lewis acid-base definitions include reactions having nothing to do with protons. Following are some examples of Lewis acid-base reactions. Notice that the common Br0nsted-Lowry acids and bases also fall under the Lewis definition, with a proton serving as the electrophile. Curved arrows (red) are used to show the movement of electrons, generally from the nucleophile to the electrophile. 

This electrophile/nucleophile dichotomy can be looked upon as a special case of the acid/base idea. The classical definition of acids and bases is that the former are proton donors, and the latter proton acceptors. This was made more general by Lewis, who defined acids as compounds prepared to accept electron pairs, and bases as substances that could provide such pairs. This would include a number of compounds not previously thought of as acids and bases, e.g. boron trifluoride (39),... 

Our approach was outlined in the framework of the Hard-Soft Acid-Base theory (HSAB, Ref. 90). In a short definition, the HSAB theory states that hard nucleophiles prefer to react with hard electrophiles and soft nucleophiles prefer to react with soft electrophiles. 

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 indeed a correlation between electrophilicity/nucleophilicity and Lewis acidity/basicity. Lewis bases are electron donors and behave as nucleophiles, whereas Lewis acids are electron acceptors and behave as electrophiles. Therefore, much of organic chemistry is explainable in terms of acid-base reactions. The main difference is that the terms nucleophile and electrophile are used when bonds to carbon are involved. We ll explore these ideas in more detail in Chapter 10. 

It soon became clear that these two classes should be called hard and soft electrophiles, respectively. Since the terms nucleophile and electrophile refer to rates of reaction, by definition, the acid-base reaction involved is... 

All nucleophiles are bases (1). In fact, within the definition of Lewis (2), nucleophilicity is basicity. Following Ingold (3), however, physical-organic chemists have normally used the Brpnsted-Lowry definition (4, 5) of bases as affinity for protons. Likewise, nucleophilicity referred to affinity for nuclei of other elements, most often carbon (3). Another classification reserves basicity, and its counterpart acidity, for equilibrium measurements, while nucleophilicity and its counterpart electrophilicity refer to rate measurements (6). The terms carbon basicity and hydrogen nucleophilicity have been employed (7-9). This classification does not seem to have gained much acceptance. 

Many chemical reactions involve a catalyst. A very general definition of a catalyst is a substance that makes a reaction path available with a lower energy of activation. Strictly speaking, a catalyst is not consumed by the reaction, but organic chemists frequently speak of acid-catalyzed or base-catalyzed mechanisms that do lead to overall consumption of the acid or base. Better phrases under these circumstances would be acid promoted or base promoted. Catalysts can also be described as electrophilic or nucleophilic, depending on the catalyst s electronic nature. Catalysis by Lewis acids and Lewis bases can be classified as electrophilic and nucleophilic, respectively. In free-radical reactions, the initiator often plays a key role. An initiator is a substance that can easily generate radical intermediates. Radical reactions often occur by chain mechanisms, and the role of the initiator is to provide the free radicals that start the chain reaction. In this section we discuss some fundamental examples of catalysis with emphasis on proton transfer (Brpnsted acid/base) and Lewis acid catalysis. 

The Lewis definitions of acid-base interactions are now over a half a century old. Nevertheless they are always useful and have broadened their meaning and applications, covering concepts such as bond-formation, central atom-ligand interactions, electrophilic-nucleophilic reagents, cationic-anionic reagents, charge transfer complex formation, donor-acceptor reactions, etc. In 1923 Lewis reviewed and extensively elaborated the theory of the electron-pair bond, which he had first proposed in 1916. In this small volume which had since become a classic, Lewis independently proposed both the proton and generalized solvent-system definitions of acids and bases. He wrote ... 

While the Bronsted acid/base terms specifically refer to proton donors and acceptors, respectively, the Lewis approach (named after G. N. Lewis, who introduced the idea in 1923) greatly broadens the definitions of what is an acid and what is a base. Recall that a Lewis acid is an electron pair acceptor and a Lewis base is an electron pair donor. All common organic reactions that do not involve radicals or concerted pericyclic processes can in some manner be discussed as Lewis acid-base reactions. Similarly, all these reactions can be considered to be occurring between electrophiles and nucleophiles. Recall that an electrophile is any species seeking electrons and a nucleophile is any species seeking a nucleus (or positive charge) toward which it can donate its electrons. In this context, a Lewis base is synonymous with a nucleophile, and a Lewis acid is synonymous with an electrophile it just de-... 

There are at least three different definitions and vantage points that chemists use to expand upon the electrostatic paradigm. They are nucleophile-electrophile combinations, Lewis acid-base reactions, and donor-acceptor orbital interactions. We have used these terms repeatedly throughout this book because they are presented in introductory organic chemistry classes, but here we give them strict definitions. Each of these definitions is a subtle variation on the other, and often it is essentially a case of semantics to decide which best describes a particular reaction. 

Gilbert N. Lewis recognized the similarity in behavior of boron tri-fiuoride and a transferred proton toward a base, and in 1923 enunciated a definition of acid-base reaction in terms of sharing of an electron pair—fl base donates an electron pair in covalent bonding and an acid accepts the pair. The acid is called an ELECTROPHILE, and the base is called a nucleophile. In the base, the atom with the unshared pair of electrons is an electron-rich site, and, in the acid, the atom that accepts the pair of electrons to form a covalent bond is an electron-deficient site. The Lewis theory focuses attention on the electron pair rather than on the proton, and in so doing broadens the concept of acidity. The transferred proton of a so-called Brbnsted acid is a special case of a Lewis acid. 

When a Br nsted base functions catalytically by sharing an electron pair with a proton, it is acting as a general base catalyst, but when it shares the electron with an atom other than the proton it is (by definition) acting as a nucleophile. This other atom (electrophilic site) is usually carbon, but in organic chemistry it might also be, for example, phosphorus or silicon, whereas in inorganic chemistry it could be the central metal ion in a coordination complex. Here we consider nucleophilic reactions at unsaturated carbon, primarily at carbonyl carbon. Nucleophilic reactions of carboxylic acid derivatives have been well studied. These acyl transfer reactions can be represented by... 

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... 

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 ... 

Model Definition. The HSAB model classifies Lewis acids (electrophiles) and bases (nucleophiles) as either "hard" or "soft." Hard acids and bases are relatively small, and exhibit low polarizability and a comparatively low tendency to form covalent bonds. Soft acids and bases have the opposite characteristics (24). Stated simply, the model postulates that hard acids react most readily with hard bases, and soft acids react most readily with soft bases (26). 

Cage, solvent, 134 Cancellation assumption. 447 Catalysis, 263 acid, 453 buffer, 269 definitions of, 263 electrophilic, 265 general acid, 265, 268 general base, 265, 268, 271 intermolecular, 266 intramolecular, 266 nucleophilic, 266, 268, 271... 

A definite connection exists between the concepts of acids and bases and the idea of nucleophiles and their complementary substances, electrophiles. A Lewis acid is an electrophile, and a Lewis base is a nucleophile. Catalysis by enzymes, including their remarkable specificity, is based on these well-known chemical principles operating in a complex environment. 

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