ABSTRACT
This chapter describes the preparation of organic ion radicals as well as their properties, i.e., electronic structure, reactivity, and interaction with counterions.
In the synthetic chemistry of organic compounds, liquid-phase reactions are most typical. Under these conditions, ion radical salts appear to be surrounded with solvate shells. Either the solvent can solvate the individual ions (having cation and anion individually surrounded by solvent molecules) or an ion pair may be solvated without solvent molecules between the ions. Further transformations of ion radicals (their disintegration, interaction with reagents directly or after the disintegration) also take place in solvents. Formation of transient states and stabilization of final products occur in solvents, too. Medium effects on the generation and structure of ion radicals are of great experimental and theoretical interest (see, for example, Orlov et al. 2001). The nature of the solvent determines the efficiency of the chosen method for ion radical generation. That is why this chapter examines the peculiarities of organic compounds as ion radical precursors under the conditions of liquid-phase electron transfer.
