Phosphorus–nitrogen compounds: novel spiro-cyclophosphazenic lariat (PNP-pivot) ether derivatives. Structures of 4,4,6,6-tetrachloro-2,2-[3-oxa-1,5-pentane dioxy bis(2-phenylamino)]cyclo-2l5,4l5,6l5-triphosphazene and 4,4,6,6-tetrachloro-2,2-[1,2-xylylene

The condensation reactions of N2Ox (xZ2, 3) donor type bifunctional aminopodands 1–4 with hexachlorocyclotriphosphazatriene, N3P3Cl6, have been investigated and the partly substituted 5–8 novel spiro-cyclic phosphaza (PNP) lariat ethers, having various different ring sizes between 11 and 14-membered macrocycles, have been prepared. Compounds 5–8 are the first examples of the spiro-cyclic phosphaza (PNP) lariat ether derivatives consisting of the aminopodand precursors. Interestingly, in the macrocyclic rings of the compounds 5–8, there are four-centered (trifurcate) N–H/O/N–H/N hydrogen bonds. The relative radii of the ring inner-hole sizes for 5–8 are 1.14, 0.95, 1.14 and 1.38 A ° . Salient futures of the spectral data (1H-, 13C-, 31P-NMR, HETCOR, FTIR and MS) are presented. The molecular structures of compounds 7 and 8 were determined by X-ray diffraction techniques. q 2005 Elsevier B.V. All rights reserved