ChemInform Abstract: Self‐Propagating Metathesis Routes to Metastable Group 4 Phosphides.

Abstract

Self-Propagating Metathesis Routes to Metastable Group 4 Phosphides.-Group 4 phosphides MP (M: Ti, Zr, Hf) are synthesized in self-propagating metathesis (exchange) reactions from Na 3 P and the metal halides MCl 4 (M: Zr, Hf) or TiI 4 . The reactions are carried out in a stainless steel reaction vessel and are ignited with a hot wire. Reactions are also carried out in sealed evacuated quartz tubes at 1000 • C for 18 h. The products are characterized by powder XRD. Whereas sealed tube reactions lead exclusively to the low-temperature hexagonal phase of MP, the self-propagating reactions lead to the high-temp. metastable cubic phase of ZrP and HfP. The process by which the cubic phases form is discussed. -(JARVIS JR., ROBERT F.; JACUBINAS, RICHARD M.; KANER, RICHARD B.; Inorg. Chem. 39 (2000) 15, 3243-3246;