Abstract: | As12Se44—: a New Selenoarsenate Anion with a Polyarsenic Cage in the Compound [Co(NH3)6]2As12Se4 · 12 NH3 Orange coloured crystals of [Co(NH3)6]2As12Se4 · 12 NH3 were prepared by the reduction of As4Se4 with a solution of sodium in liquid ammonia and subsequent precipitation with CoBr2. The X‐ray structure determination shows them to contain the selenoarsenate anion As12Se44—, which consists of a central As12‐cage with four exo‐bonded, formally negatively charged Se atoms. The structure of the As12‐cage is equivalent to the main polyphosphorus building unit of a known organopolyphosphane and of tubular P12 in the compound (CuI)3P12. |