Bi(cyclophosphazenes) (2) react with nucleophiles such as sodium trifluoroethoxide or sodium phenoxide by two alternative pathways—(a) with cleavage of the PP ring linkage unit and cleavage of PCl bonds to yield organocyclotriphosphazenes (3) or (b) by cleavage of PCl bonds without rupture of PP bonds to give organobi(cyclophosphazenes) (6). These latter species eventually undergo PP bond scission with alkoxides or aryl oxides under more forcing reaction conditions. Cleavage of the bi(cyclophosphazenes) 2 or 6 also yields phosphazene anions (4), which react with alcohols to form hydridocyclotriphosphazenes (5). Treatment of these with chlorine brings about the conversion of the PH to PCl units. The phosphazene anions (4) also react with allyl bromide with attachment of the allyl residue to the ring and with carbon tetrachloride to abstract Cl+ and generate neutral chloroorganocyclotriphosphazene species (9). These interconnected processes were monitored by both product isolation and NMR spectroscopy. Appendices A and B (supplementary material) outline the interpretation of the more complex 1H and 31P NMR coupling patterns observed.
All Science Journal Classification (ASJC) codes
- Colloid and Surface Chemistry