By adapting a combination of literature procedures for the synthesis of P(SiMe3)3 from PNa3 with 3 eq. ClSiMe3, the salt metathesis reaction of PNa3 (prepared in situ from red phosphorus, sodium metal and naphthalene) with 3 eq. ClSi i Pr3 in DME at reflux for 24 h gave [Na{P(Si i Pr3)2}]n as a white powder in 45% crude yield following work-up. A small . This method represents a convenient entry point to {P(Si i Pr3)2} coordination chemistry starting from red phosphorus, where previously PH3 was used as a starting material (see above). The separate salt metathesis reactions of ). We find that for 1-Ln elemental analysis results are generally in good agreement with predicted values, but the carbon values obtained were reproducibly lower than expected; we attribute this observation to incomplete combustion arising from carbide formation, which is a common feature for analogous Ln {N(Si i Pr3)2} and Ln {P(SiMe3)2} complexes.