PREPARATION AND CHARACTERIZATION OF A MATERIAL OF COMPOSITION BIP (BISMUTH PHOSPHIDE) AND OTHER INTERGROUP-15 ELEMENT PHASES

The reaction between equimolar quantities of BiCl3 and the silylphosph ine P(SiMe3)(3) in toluene or THF (tetrahydrofuran) solution affords a black precipitate with the composition of bismuth phosphide, BiP, whi ch has been examined by EDXA, SEM, XPS, powder XRD, solid-state P-31 N MR spectroscopy, and elemental analysis. Alternative possible routes t o BiP involving the reactions between Na3P and BiCl3 and between Bi(NM e2)(3) and P(SiMe3)(3) have also been investigated, both of which affo rd black powders of composition close to BiP, although in the latter c ase there is some contamination with bismuth metal. Analogous reaction s with either SbCl3 or AsCl3 and P(SiMe3)(3) afford black and dark bro wn precipitates, respectively, which are formulated as the materials a ntimony phosphide, SbP, and arsenic phosphide, AsP, on the basis of si milar analyses. Preliminary experiments have also shown that the relat ed arsenides, BiAs and SbAs, can be prepared from reactions between ei ther BiCl3 or SbCl3 and the silylarsine As(SiMe3)(3), and that a terna ry phase with the composition BiSbP2 is formed in the reaction between BiCl3, SbCl3, and P(SiMe3)(3) in a 1:1:2 mole ratio. A material of co mposition close to elemental phosphorus is obtained from the reaction between PCl3 and P(SiMe3)(3).