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.

Radical mechanism of alkylation of sodium naphthalenide

Single electron transfer and nucleophilic substitution

3.1.5. Spectroelectrochemistry 2189 3.2. Photochemical Initiation 2190 3.2.1. Laser Flash Photolysis 2190 3.3. Initiation by Solvated Electrons 2190 3.3.1. Pulse Radiolysis 2191 3.4. Thermal Homogeneous Electron Transfer 2191 3.4.1. Self-Exchange Electron Transfer 2191 3.4.2. Stop Flow 2191 3.4.3. Continuous Flow 2191 4. Electron Transfer Reactions: Fundamental Aspects and Experimental Examples 2192

Electron transfer initiated reactions: bond formation and bond dissociation.

Electron transfer, naphthalene radical anion, and alkyl halides

One electron more, One electron less. What does it change? Activations Induced by electron Transfer. The electron, an activating messenger.

Since the classical studies by Ingold in the nineteen thirties the mechanism of the aliphatic nucleophilic substitution reaction has been described as a polar two-electron mechanism in which the nucleophile transfers two electrons to the new bond which is established to the electrophilic center. Depending on the reaction order the abbreviations SN1 and SN2 were used for first-order and second-order reactions, respectively.

Radical mechanism of alkylation of sodium naphthalenide

Citations

Single electron transfer and nucleophilic substitution

Electron transfer initiated reactions: bond formation and bond dissociation.

Electron transfer, naphthalene radical anion, and alkyl halides

One electron more, One electron less. What does it change? Activations Induced by electron Transfer. The electron, an activating messenger.

Single Electron Transfer in Aliphatic Nucleophilic Substitution

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