Synthesis and coordination chemistry of pyrimidine-substituted phosphine ligands

► The synthesis of the uracil(Ur)-substituted phosphine PPh2Ur is described. ► The uracil group dictates the 3-D topology of the phosphine in the solid state. ► PPh2Ur is shown to act as a ligand to copper(I) in [Cu4(μ3-I)4(PPh2Ur)4]. ► A related phosphine containing a protected uracil group (PPh2UrP) is described.