Phosphorus−Nitrogen Compounds. Part 13. Syntheses, Crystal Structures, Spectroscopic, Stereogenic, and Anisochronic Properties of Novel Spiro-Ansa-Spiro-, Spiro-Bino-Spiro-, and Spiro-Crypta Phosphazene Derivatives

The condensation reactions of N2Ox (x = 2, 3) donor-type aminopodand (4) and dibenzo-diaza-crown ethers (5,
6, and 9) with hexachlorocyclotriphosphazatriene, N3P3Cl6, produce two kinds of partially substituted novel
phosphazene derivatives, namely, spiro-bino-spiro- (19) and spiro-crypta (21, 22, and 25) phosphazenes. The
partially substituted spiro-ansa-spiro-phosphazene (11) reacted with pyrrolidine and 1,4-dioxa-8-azaspiro[4,5]decane
(DASD) give the corresponding new fully substituted phosphazenes (14 and 16). Unexpectedly, the reactions of 23
and 24 with pyrrolidine result in only geminal crypta phosphazenes (26 and 27). The solid-state structures of 16
and 22 have been determined by X-ray diffraction techniques. The relative inner hole-size of the macrocycle in the
radii of 22 is 1.27 Å. The relationship between the exocyclic NPN (α‘) and endocyclic (α) bond angles for spiro-crypta phosphazenes and exocyclic OPN (α‘) bond angles for spiro-ansa-spiro- and spiro-bino-spiro-phosphazenes
with 31P NMR chemical shifts of NPN and OPN phosphorus atoms, respectively, have been investigated. The
structures of 10, 14, 16, 19, 21, 22, and 25−27 have also been examined by FTIR, 1H, 13C, and 31P NMR, HETCOR,
MS, and elemental analyses. The 31P NMR spectra of 10, 21, 22, and 25 indicate that the compounds have
anisochrony. In compounds 16 and 22, the spirocyclic nitrogen atoms have pyramidal geometries resulting in
stereogenic properties.