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

The coordination and functionalization of white phosphorus (P) 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)][(Cp''Ln)(μ-ƞ:ƞ:ƞ:ƞP)], which was isolated along with [K(18-crown-6)][(Cp''Ln)(μ-ƞ:ƞP)] (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.