Publisher Summary This chapter focuses on the electron transfer reactions in organic chemistry. The simplest elementary act in homogeneous solution chemistry is the exchange of an electron between two chemical entities. No bonds need to be formed or broken in the process, and if the two species are identical, except for a difference in oxidation state, no net chemical change takes place. Such self-exchange reactions constitute the basis of theoretical treatments of electron transfer. A more complex and chemically interesting situation is the electron-transfer reaction between two species of different chemical composition. In electron-transfer theory, it is an important postulate that electrons are transferred one by one, which does not mix well with the two-electron centered electronic theory of organic molecules. Organic electron transfers rarely occur as isolated steps because of the high chemical reactivity of odd-electron species. Processes involving one or several electron-transfer steps are not likely to preserve the stereochemical integrity of the reactants. With the present upsurge of research studies frequently invoking organic electron-transfer steps in mechanistic discussions, there is a great need of a theoretical background applicable to organic species and compatible with the language of physical organic chemistry.

Electron transfer reactions in organic chemistry

Polarography is still the best known classical measuring method in electroanalytical chemistry. However, in recent years its position has been challenged by cyclic voltammetry (CV). Simple diagnostic criteria and relatively easily acquired measuring techniques have hastened this development. Cyclic voltammetry has the further attraction of providing information not only on the thermodynamics of redox processes but also on the kinetics of heterogeneous electron-transfer reactions and coupled chemical reactions. The characteristic shapes of the voltammetric waves and their unequivocal position on the potential scale virtually fingerprint the individual electrochemical properties of redox systems. For this reason the method has been labeled “electrochemical spectroscopy”.

Cyclic Voltammetry—“Electrochemical Spectroscopy”. New Analytical Methods (25)

Nucleophilic substitution reactions by electron transfer

Catalysis of chemical reactions by electrodes

Publisher Summary This chapter discusses single electron transfer and nucleophilic substitution. The SRNl reaction appears as a reaction in which single electron transfer plays a pre-eminent role but is by no means a single elementary step. A different problem is that of the possible involvement of single electron transfer in reactions that are not catalyzed by electron injection (or removal). A typical example of such processes is another substitution reaction—namely, the SN2 reaction. The chapter discusses the reactions in which electron transfer is associated with the breaking of a bond but in which either no bond formation occurs or, if it does, it takes place in aseparated step. There are a number of cases where “true” SN2 mechanisms (in which the bond-breaking and bond-formation steps are concerted) do occur, even with nucleophiles that are members of reversible one-electron reversible redox couples.

Single electron transfer and nucleophilic substitution

Electrochemical inducement of aromatic nucleophilic substitution of ArX compounds is investigated for a number of substrate and nucleophile systems in liquid ammonia. Electron transfer to the Armradical resulting from the initial reductive cleavage is essentially the only reaction competing with substitution. The competition occurs under two different regimes in- volving either homogeneous or heterogeneous electron transfer leading to different kinds of kinetic control. Cyclic voltammetry is used both for a rapid estimate of the nucleophile reactivity and for a quantitative determination of the rate constants of the nucleophile addition on Are. The method is also applied to the determination of the kinetic stabilities of the substrate anion rad- icals which is not possible through the standard application of electrochemical techniques. The agreement of the predicted ki- netics with the experimental data both under homogeneous and heterogeneous electron transfer conditions provides further support for the SRNI mechanism.

Electrochemically induced aromatic nucleophilic substitution in liquid ammonia. Competition with electron transfer

Electrochemically Induced Aromatic Nucleophilic Substitution in Liquid Ammonia. Competition with Electron Transfer

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Electrochemically induced aromatic nucleophilic substitution in liquid ammonia. Competition with electron transfer

Electrochemically Induced Aromatic Nucleophilic Substitution in Liquid Ammonia. Competition with Electron Transfer