[Li{μ-P(Si i Pr3)2}(THF)]2, was prepared by the deprotonation of HP(Si i Pr3)2 with n BuLi in THF. Further to this, [Li(PH2)(DME)] was synthesized from highly toxic gaseous PH3, and a synthetic route from more readily available red phosphorus has not yet been disclosed; this advance has allowed the chemistry of the smaller phosphide Pʹʹ to be developed more rapidly (see above), though this still typically involves the large scale synthesis of P(SiMe3)3 via PNa3, which requires specialist glassware and protocols. Here we report the synthesis of the first structurally authenticated Ln(II) {P(Si i Pr3)2}