Chlorine trioxide, Cl2O6, a most efficient perchlorating reagent in new syntheses of anhydrous metal perchlorates, chloryl and nitryl perchloratometalates of cobalt(II), nickel(II), and copper(II). Reactivity of chlorine trioxide with anhydrous or hydrated chlorides and nitrates

Abstract

Anhydrous transition-metal perchlorates, M(ClO4)2(M = Ni, Co, or Cu), and their chloryl and nitryl salts, ClO2M(ClO4)3, NO2M(ClO4)3, and (NO2)2M(ClO4)4, have been prepared by the action of Cl2O6 on the corresponding anhydrous or hydrated metal chloride or nitrate. The intermediate chloryl salts, ClO2M(ClO4)3, can be isolated. The formation of NO2+ is due to the highly acidic medium. The vibrational spectra of the compounds M(ClO4)2 suggest a strong metal–perchlorate interaction and are consistent with the presence of two types of bidentate perchlorate group in Cu(ClO4)2 and tridentate perchlorate in Ni(ClO4)2 and Co(ClO4)2. The electronic spectra indicate an octahedral environment around the metal atom, and a polymeric structure.