Structure and reactivity of derivatives of dihalogenomethyl indium(III) halides, X2InCHX2 (X = Cl, Br, I)

The reactions of indium monohalides, InX with haloforms, CHX3, in 1,4-dioxane (diox), produce the dioxane adducts of dihalogeno–dihalogenomethyl–indium(III), X2In(diox)nCHX2 (X = Cl, Br, n = 1; X = I, n = 2) compounds. The ionic derivative [(C2H5)4N] [Cl3InCHCl2] was prepared and its crystal structure determined by X-ray means. The reactions of the X2In(diox)nCHX2 compounds are significantly different from those of the related X2InCH2X compounds. The dihalogenomethyl derivatives react with strong electrophiles suggesting dihalogenomethyl substituents of mild nucleophilic character, while the carbon atoms in the halogenomethyl derivatives are electrophilic.