Electronic Structure-Reactivity Relationship in Ion-Radical Organic Chemistry

This chapter considers ion-radicals with detained and released single electrons. Some ion-radicals contain fragment orbitals that suspend an unpaired electron preferentially. Other ion-radicals are characterized by the delocalization of an unpaired electron along orbitals, which encompass the whole molecular framework more or less evenly. This chapter considers the material, comprised from this point of view, using the terms detained and released electron. Such an abstraction helps us to analyze these two intrinsic features of organic ion-radical reactivity. 

Section 3.2 includes an extensive discussion on the formation of odd-electron bonds, ion pairing, and the distonic stabilization of ion-radicals at the expense of separation between their spins and charges. Section 3.3 deals with ion-radicals from the class of even spin-charge distribution. This class occnrred more frequently in scientific works of past decades. However, the reader will find newly developed manifestations of the principle of the released electron, concerning spread conjugation and the fates of ion-radical precursors with increased dimensionality. 

It is obvions that any categorization tends to name the main trait of the phenomenon under consideration. This is useful. At the same time, the categorization need not be understood literally becanse each effect possesses multiple characteristics. However, it is impossible to study anything withont even a minimal classification. In fact, investigations on the ion-radical electronic structure appear to be more developed than studies on their reactivity. Therefore, not every example considered here is snpplied with the reactivity description. However, future accomplishments in studies on ion-radical reactions will be better understood in terms of the principles stated here. 

Section 3.4 is devoted to organic ion-radical behavior in living organisms. Particularly, the consideration of an ion-radical mechanism of carcinogenesis reflects a point of view, which is new, and, in many respects, promising. 

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