Unusual products in the reactions of hexachlorocyclotriphosphazatriene with sodium aryloxides


KILIC A., BEGEC S., CETINKAYA B., Hokelek T. , KILIC Z., GUNDUZ N., ...More

HETEROATOM CHEMISTRY, vol.7, no.4, pp.249-256, 1996 (Journal Indexed in SCI) identifier identifier

  • Publication Type: Article / Article
  • Volume: 7 Issue: 4
  • Publication Date: 1996
  • Title of Journal : HETEROATOM CHEMISTRY
  • Page Numbers: pp.249-256

Abstract

Reactions of hexachlorocyclotriphosphazatriene, N3P3Cl6 1, with sodium aryloxides have been studied. Compound 1 was found to react by the nucleophilic substitution path way to yield monocyclophosphazenes [N3P3Cl5(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 cyclotriphosphazene rings linked by a P-P bond [2.193 (2) Angstrom], which have been obtained by reacting 1 with ArONa. The structures of compounds 5-8 ave ascertained by elemental analyses, H-1-, P-31-C-13-NMR, IR, and MS spectra. The molecular structure of monocyclic-phosphazene 5 was determined by X-ray diffraction techniques for further structural assignment. It crystallizes in the monoclinic space group P2(1)/m with a = 6.144(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 there is only a half molecule in the asymmetric unit. (C) 1996 John Wiley & Sons, Inc.