REACTIVITY AND POLYMERIZATION BEHAVIOR OF A PENTACHLOROCYCLOCARBOPHOSPHAZENE, N3P2CCL5

The cyclic carbophosphazene N3P2CCl5 reacts with sodium methoxide, sod ium trifluoroethoxide, and sodium phenoxide to yield the corresponding pentaalkoxy- and pentakis(aryloxy)cyclocarbophosphazenes. By contrast , N3P2CCl5 does not react with the main group and transition metal nuc leophiles lithium diphenylphosphide and lithium pentacarbonylmanganate and reacts incompletely with sodium dicarbonyl(eta5-2,4-cyclopentadie n-1-yl)ferrate. The title compound undergoes thermal ring-opening poly merization when heated to 120-degrees-C. This polymerization was monit ored by P-31 NMR spectroscopy. Aspects of the mechanism of polymerizat ion are discussed. Crystal structures of N3P2CCl5 and N3P2C(OPh)5 were obtained by X-ray diffraction. The crystals of N3P2CCl5 are orthorhom bic, of space group Pbca, with a = 7.7880 angstrom, b = 29.3560 angstr om, c = 16.7990 angstrom, beta = 90.00-degrees, V = 3840 angstrom3, an d Z = 16, whereas crystals of N3P2C(OC6H5)5 are triclinic, of space gr oup P1BAR, with a = 10.249(2) angstrom, b = 12.290(4) angstrom, c = 14 .437(2) angstrom, alpha = 84.65(2)degrees, beta = 85.57(1)degrees, gam ma = 70.82(2)degrees, V = 1708.08 angstrom3, and Z = 2.