REACTIONS OF P4S3I2 WITH BIFUNCTIONAL LIG ANDS

Nitrogen, oxygen, selenium or carbon atoms were introduced as bridges into the P4S3 Skeleton by the reaction of alpha- or beta-P4S3I2 with b ifunctional ligands. Among compounds in the series alpha-P4S3-mu-E, th e oxide alpha-P4SO was made for the first time. High concentrations of alpha-P4S4Se, made by a new route, allowed observation of Se-77 satel lites in its P-31 NMR spectrum and hence the assignment of P-31 chemic al shifts. Polymeric species were more stable than these monomers, lea ding to low yields in both reactions. alpha- and beta-isomers of P4S3I 2 reacted with diethyl malonate. While beta-P4S3I2 gave traces of beta -P4S3(CR(2))(R = C2H5CO2) and of beta-P4S3(CHR(2))(exo)(CHR2)(endo), a long with insoluble products, alpha-P4S3I2 yielded alpha-P4S3(CR(2)), which could be isolated. P4S2(CR(2)), a new skeleton similar to that o f P4S3, was formed on storage of CS2 solutions of a-P4S3(CR(2)) for tw o days. The P-31 NMR data of the molecules are given.