ABSTRACT

This chapter describes the preparation of organic ion-radicals in relation to its properties, that is, electronic structure, reactivity, and interaction with counterions. In synthetic chemistry of organic compounds, liquid-phase reactions are most typical. Under these reaction conditions, ion-radical salts appear to be surrounded with solvate shells. Solvents can either solvate the individual ions (having cation and anion individually surrounded by solvent molecules) or an ion pair may be solvated as a whole, without solvent molecules between the ions. Further transformations of ionradicals (their disintegration, interaction with reagents directly or after the disintegration) and formation of transient states and stabilization of nal products also take place in solvents. Medium effects on the generation and structure of ion-radicals are of signi cant interest for experimental and theoretical levels of studies (see, e.g., Orlov et al. 2001). The nature of the solvent de nes the ef ciency of the chosen method for ion-radical generation. This chapter examines the peculiarities of organic compounds as ion-radical precursors under the conditions of the liquid-phase electron transfer.