UNUSUAL PRODUCTS IN THE REACTIONS OF HEXACHLOROCYCLOTRIPHOSPHAZATRIENE WITH SODIUM ARYLOXIDES

Reactions of hexachlorocyclotriphosphazatriene, N3P3Cl6 1, with sodium aryloxides have been studied. Compound 1 was found to react by the nu cleophilic substitution path way to yield monocyclophosphazenes [N3P3C l5(OC(6)H(2)Bu(3)(t)-2, 4, 6) 5 and N3P3Cl4(OC(6)H(2)Me-4-Bu(2)(t)-2, 6)(2) 6] and bi(cyclophosphazenes) ([Cl5N3P3-P3N3Cl4(OC(6)H(3)Bu(2)(t) -2, 6)] 7 and [N3P3(OC(6)H(3)Bu(2)(t)-2, 6)(5)](2) 8]. The unusual bi( cyclophosphazenes) 7 and 8 are the first examples of two cyclotriphosp hazene rings linked by a P-P bond [2.193 (2) Angstrom], which have bee n obtained by reacting 1 with ArONa. The structures of compounds 5-8 a ve ascertained by elemental analyses, H-1-, P-31-C-13-NMR, IR, and MS spectra. The molecular structure of monocyclic-phosphazene 5 was deter mined by X-ray diffraction techniques for further structural assignmen t. It crystallizes in the monoclinic space group P2(1)/m with a = 6.14 4(2), b = 17.079(9), c = 13.181(9) Angstrom, beta = 92.79(7), and Z = 2, R = 0.074. Compound 5 is on a crystallographic mirror plane, and th ere is only a half molecule in the asymmetric unit. (C) 1996 John Wile y & Sons, Inc.