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.