Department of Chemistry, Indian Institute of Technology, Madras-600 036 Methods of generation of a few inorganic radicals by irradiation are briefly reviewed and their properties discussed. The carbonate radical is dealt with in some detail. Its modes of reaction with several types of organic substrates, such as aromatic amines, aliphatic open chain amines and cyclic amines with bridgehead nitrogen atoms are discussed. Carbo­nate radical forms an adduct with anilines via electrophilic attack,

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... e data suggesting that an ipso carbon attack is the initial step. The adduct disso­ciates into ArNH2+ (cation) and co\(_3^{2-}\) giving rise to the photoproducts. Aliphatic amines react by a dual mechanism, viz. (i) hydrogen abstraction and (ii) electron transfer. Tertiary amines react via electron transfer. Primary and secondary amines react probably by hydrogen abstraction. Cyclic amines with bridgehead nitrogen atoms display widely different reactivities. These differences are explained in terms of 'Through Bond Resonance' concept of Hoffmann.