Molecular -P complexes of the rare-earth elements a one-pot reaction and selective reduction.

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