Synthesis of Molecular Organo‐f‐Element‐Polyphosphides with Nonclassical Divalent Lanthanide Precursors

The coordination and functionalization of white phosphorus (P4) by transition metal and main group element compounds have led to a great variety of polyphosphides. However, larger polyphosphides of the rare-earth elements are elusive. In this study, we report the synthesis and full characterization of the largest polyphosphides of the f-elements, [K(18-crown-6)]2[(Cp′′2Ln)2(μ4-ƞ2:ƞ2:ƞ2:ƞ2P14)], which was isolated along with [K(18-crown-6)][(Cp′′2Ln)2(μ-ƞ3:ƞ3P3)] (Ln = La, Ce, Cp′′ = 1,3-bis(trimethylsilyl)cyclopentadienyl). These compounds were obtained by using nonclassical divalent compounds of the early lanthanides for the reduction of white phosphorus.