We present the first one-step synthesis of a source of the phosphanide anion [P(Si i Pr3)2] -, in the form of NaP(Si i Pr3)2 (1). Complex 1 was obtained in 42% isolated yield, far higher than the previously reported Li phosphanide [(THF)LiP(Si i Pr3)2]2, thereby offering a significantly improved route to the practical use of this ligand in synthesis. [(THF)NaP(Si i Pr3)2], 1a obtained from the solvation of 1 in THF, was characterized by single crystal X-ray diffraction. With this synthetically useful methodology to 1, we were able to complex this sterically demanding phosphanide ligand to Zn, Cd, and Hg, affording the novel two-coordinate complexes 2-4. Single crystal X-ray diffraction revealed that complexes 2-4 all show significant deviations from linearity in the solid state, with DFT calculations suggesting this is due to the steric demands of the ligand. C{ 1 H} and 29 Si{ 1 H} NMR spectroscopy of these ligands revealed strong second-order effects, suggesting the presence of virtual coupling between the two 31 P nuclei in these complexes. These studies show that [P(Si i Pr3)2] -is now an accessible bulky, monodentate, monoanionic ligand.