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

Abstract The coordination and functionalization of white phosphorus (P 4 ) 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′′ 2 Ln) 2 ( μ 4 ‐ ƞ 2 : ƞ 2 : ƞ 2 : ƞ 2 P 14 )], which was isolated along with [K(18‐crown‐6)][(Cp′′ 2 Ln) 2 ( μ ‐ ƞ 3 : ƞ 3 P 3 )] (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.