ASPECTS OF THE COORDINATION CHEMISTRY OF THE ORGANOCHLOROPHOSPHORANE P (CHCL2) CL4 AND OF ITS TETRACHLOROALUMINATE SALT [P (CHCL2) CL3] [ALCL4]

The phosphorane P(CHCl2)Cl4 has been synthesised, and shown to have a molecular psi-tbp structure. It accepts chloride ions to form the [P(CHCl2)Cl5]- ion, which slowly with excess AgCN to give the fully-substituted organocyanophosphate ion [P(CHCl2)(CN)5]-. Several intermediate chlorocyanophosphates have been identified in solution by P-31 NMR spectroscopy, and isomeric configurations have been assigned to these by the method of pairwise interactions. The pattern of substitution is discussed and compared with those for related species. An unstable cationic complex [P(CHCl2)Cl3 bipy]+ has been obtained in solution by reaction of [P(CHCl2)Cl3][AlCl4] with 2,2'-bipyridine (bipy).