Molecular cyclo-P3 complexes of the rare-earth elements via a one-pot reaction and selective reduction

Abstract

Synthesis of new organo-lanthanide polyphosphides with an aromatic cyclo-[P₄]²⁻ moiety and a cyclo-[P₃]³⁻ moiety is presented. For this purpose, the divalent Ln^II-complexes [(NON)Ln^II(thf)₂] (Ln = Sm, Yb) ((NON)²⁻ = 4,5-bis(2,6-diisopropylphenyl-amino)-2,7-di-tert-butyl-9,9-dimethylxanthene) and trivalent Ln^III-complexes [(NON)Ln^IIIBH₄(thf)₂] (Ln = Y, Sm, Dy) were used as precursors in the reduction process of white phosphorus. While using [(NON)Ln^II(thf)₂] as a one-electron reducing agent the formation of organo-lanthanide polyphosphides with a cyclo-[P₄]²⁻ Zintl anion was observed. For comparison, we investigated a multi-electron reduction of P₄ by a one-pot reaction of [(NON)Ln^IIIBH₄(thf)₂] with elemental potassium. As products molecular polyphosphides with a cyclo-[P₃]³⁻ moiety were isolated. The same compound could also be obtained by reducing the cyclo-[P₄]²⁻ Zintl anion within the coordination sphere of Sm^III in [{(NON)Sm^III(thf)₂}₂(μ-η⁴:η⁴-P₄)]. Reduction of a polyphosphide within the coordination sphere of a lanthanide complex is unprecedented. Additionally, the magnetic properties of the dinuclear Dy^III-compound bearing a bridging cyclo-[P₃]³⁻ moiety were investigated.