Carbonyl dibromide: a novel reagent for the synthesis of metal bromides and bromide oxides 

Abstract

Carbonyl dibromide reacted with a wide selection of d- and f-block transition-metal oxides to form either the metal bromide or bromide oxide; the reactions are driven by the elimination of carbon dioxide. In a typical reaction the metal oxide was treated with an eight-fold excess of COBr₂ in a sealed Carius tube at 125 °C for 10 d (to ensure complete reaction of the metal oxide). As COBr₂ and the reaction by-products (CO₂, CO and Br₂) are all volatile, the desired products were obtained in essentially quantitative yield and a high degree of purity. Under these conditions V₂O₅, MoO₂, Re₂O₇, Sm₂O₃ and UO₃ were converted into VOBr₂, MoO₂Br₂, ReOBr₄, SmBr₃ and UOBr₃, respectively. This route offers great potential for the preparation of many known bromide derivatives of the transition metals, lanthanides and actinides, in a very convenient manner, and also for the synthesis of new materials. A modified synthesis of carbonyl dibromide was elaborated, and its ¹⁷O NMR and electron impact mass spectra are reported for the first time.

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