White phosphorus reacts with organic diselenides in a dipolar aprotic solvent in the presence of a base with the formation of tri(alkyl‐ or aryl‐seleno)phosphites in good yield.
Tri(methylseleno)phosphitc shows a 31P‐chemical shift = −107 ppni (JP, 77Se = 233 Hz). It is readily oxidizcd in air to the corresponding selenophosphate, (CH3Se)3 PO, 31P‐chemical shift = −16 ppm.
Tri(phenylseleno)phosphite reacts readily with mercury oxide to give the tri(phenylseleno)phosphate, a yellow solid of m.p. 105–110°. It also reacts with sulfur in refluxing benzene solution to give tri(phenylseleno)thiophosphate, also a yellow solid of m.p. 55–58°. However, an attempt to prepare tri(phenylseleno)selenophosphate failed. Under the same conditions as given above, white phosphorus also reacts with di‐p‐anisyl ditelluride to give tris(p‐anisyltelluro)phosphite, shiny, rusty brown crystals which decompose rapidly at room temperature, but are stable for several months when kept in acetonc solution at −20°.