Phosphorus-nitrogen compounds: Novel fully substituted spiro-cyclophosphazenic lariat (PNP-pivot) ether derivatives. Structures of 4,4,6,6-tetrapyrrolidino-2,2-[3-oxa-1,5-pentane dioxy bis(2-phenylamino)]cyclo-2λ5,4λ5,6λ5-triphosphazene and 4,4,6,6-tet

The condensation reaction of partly substituted spiro-cyclophosphazenic lariat (PNP-pivot) ethers, N3P3[(o-NHPhO)2R]Cl4 (5-8), where R=-CH2CH2-, -CH2CH2CH2-, -CH2CH2OCH2CH2-, and -CH2PhCH2-, with pyrrolidine have been afforded fully substituted pyrrolidino phosphazene derivatives (9-12) (Scheme). There are the first examples of the spiro-cyclophosphazenic lariat (PNP-pivot) ether ligands with N2Ox-(x=2, 3) donor type containing 11-14 membered macrocycles. The solid state structures of (11 and 12) have been determined by X-ray diffraction techniques. Evidently, in the macrocyclic ring of the compound (11), there are two three-centered (bifurcate) N-H⋯O/N-H⋯N hydrogen bonds, while compound (12) has two intramolecular N-H⋯O bonds. The relative radii of macrocyclic hole sizes of the compounds (11 and 12) are 1.25 and 1.10 Å, respectively. The structures of the new compounds (9-12) have also been examined by FTIR, 1H-, 13C-, 31P-NMR, MS and elemental analysis. Compound (11) crystallizes in the Pcab space group with a=9.8474(13), b=18.466(2), c=38.9375(19) Å, V=7080.7(14) Å3, Z=8 and Dx=1.317 g cm−3, while compound (12) crystallizes in P-1 space group with a=9.3724(5), b=11.2613(9), c=20.401(2) Å, α=93.177(8), β=102.115(7), γ=105.360(5)°, V=2016.0(3) Å3, Z=2 and Dx=1.268 g cm−3. The structures of (11 and 12) consist of nearly planar and non-planar trimeric phosphazene rings with spiro-cyclic bulky N2O3 and N2O2 macrocycles, respectively.