Abstract
The new polyphosphorus Zintl anion P22 4− has been synthesised by combining two P11 3− anions by oxidation with Br2I− in liquid ammonia. The single crystal structure analysis shows that P22 4− consists of two trishomocubane-like cages connected by a single bond. While the former method makes use of pre-formed Zintl anions extracted from solids, the second route presented involves direct reduction of the elements with the expanded metal Li(NH3)4. Reaction of Li(NH3)4 with P, As, and Sb yields [Li(NH3)4]4P14 , [Li(NH3)4]3As7 · NH3 and [Li(NH3)4]3[Li2(NH3)2Sb5] · 2 NH3. The Sb compound contains the new Zintl anion cyclo-Sb5 5− , which is stabilised in the ion complex (Li2(NH3)2Sb5)3−.
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