is known as a "standard" compound in the field of phosphazene chemistry, which has potential use in the syntheses of many small organocyclophosphazene derivatives. 1 In the reactions of N3P3Cl6 with N2O2-donor type tetradentate ligands, two kinds of products, e.g. spiro-ansa-spiro and spiro-bino-spiro, are expected to be formed. However, only the spiro-ansa-spiro architecture has been isolated. The title molecule was prepared from the reaction of N,N′bis(2-hydroxyethyl)ethylenediamine (5.00 g, 33.8 mmol), N3P3Cl6 (5.88 g, 16.9 mmol) and K2CO3 (18.65 g, 135.1 mmol) in dry THF (250 ml) by vigorous stirring; argon was passed over the reaction mixture for 2 days. The solvent was evaporated and the residue was chromatographed [eluent CH3CN-benzene (2:1), silica-gel (100 g)] and then crystallized from a CH3CN-benzene (2:1) mixture (yield 2.48 g, 47%, m.p. 528 K). The X-ray analysis results are given in Tables 1-3. The H atoms were located in a difference synthesis and refined isotropically. The title molecule is on a crystallographic mirror plane that passes through N2, P1, Cl1, and Cl2; therefore, only half of this molecule is independent. The C3 atom was disordered. The occupancies of the disordered C3A and C3B atoms were fixed at 0.5. The title molecule was also analysed to resolve the disorder in lower symmetry space group Pna21 by removing the mirror symmetry in the molecule, but was not successful. In the title molecule (Fig. 2) the rings, A(P1/N1/P2/N2/ P2 i /N1 i) and B(N2/P2/N3/C3a/C3b i /N3 i /P2 i), are not planar with total puckering amplitudes 2 of QT = 0.431(4) and 0.839(4)Å, respectively [symmetry code (i): x, 1.5-y, z]. The fivemembered ring C(P2/O1/C1/C2/N3) has a twisted conformation with ϕ2 =-80.8(5)˚. The bicyclic system is made up of rings A and B in a sofa conformation (Fig. 3a). Each ring is V-shaped. Regarding the disordered structure of the N-CC -N chain, the sums of the bond angles around the N3 atom [335.4(4) and 356.0(3)˚] show a change in the hybridization of atom N3 from x77
The title compound, C 16 H 16 Cl 2 N 5 O 2 P 3 , a cyclotriphosphazene, has a spiro±ansa±spiro architecture in which the bicyclic system is in the sofa conformation. Two P atoms and one N atom are capable of representing stereogenic centres.
The reactions of N2O2‐donor‐type aminopodands 1–3 with trimer N3P3Cl6 led to the novel spirocyclic phosphazene derivatives 4–10 (Scheme). Compounds 4–7 and 8–10 are the first examples of the substituted spiro‐ansa‐spiro and spiro‐bino‐spiro phosphazene derivatives, respectively. The pyrrolidinyl‐substituted phosphazene derivatives 7 and 10 were synthesized from 5 and 9, respectively, with an excess of pyrrolidine. The reaction of aminopodand 3 (R(CH2)4) with N3P3Cl6 in dry THF afforded only spiro‐ansa‐spiro phosphazene 6. The molecular structure of compound 9 was determined by X‐ray diffraction: it shows the novel spiro‐bino‐spiro phosphazene architecture.
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