Synthesis and characterization of the phosphorus triazides OP(N3)3 and SP(N3)3.

Two explosive triazides of phosphorus(V), OP(N(3))(3) and SP(N(3))(3), have been prepared as neat substances and structurally characterized. Both compounds can be handled in gas, liquid, and solid states in submillimolar quantities. The melting points of OP(N(3))(3) and SP(N(3))(3) are +22 and -30 °C, respectively. The two triazides have been characterized by IR (Ar matrix and gas phase) and Raman (solid) spectroscopies. Their single-crystal structures were obtained by X-ray diffraction and found to be significantly distorted from the predicted ideal C(3) symmetry because of intermolecular interactions. The spectroscopic and structural properties are discussed in combination with density functional theory calculations.