Bis[cyclotri(phosphazen)yl] oxide. / Bis[cyclotri(phosphazen)yl]oxides

Abstract

Hydrido-cyclotri(phosphazen)es can be coupled by one or two step oxidation to give symmetric and unsymmetric bis[cyclotri(phosphazen)yl]oxides. Their structure follows from the analysis of their NMR spectra

Bridged cyclophosphazenes resulting from deprotonation reactions of cyclotriphophazenes bearing a P–NH group

“…The protondecoupled 31 P NMR spectrum of the isolated product (2b) is observed as a basic AA¢BB¢XX¢-type spin system with further coupling on the two multiplets, P(NR)Cl and P spiro , due to geminal coupling of ca. 27-28 Hz across the cyclophosphazene ring similar to compound 2a 13 and in the range (23)(24)(25)(26)(27)(28)(29)(30)(31)(32)(33)(34)(35) found for other P-N-P bridged cyclophosphazenes; 19 the 31 P NMR spectrum is consistent with formation of a bis-cyclophosphazene bridged structure.…”

“…5a and b, respectively) confirmed they are bridged compounds as indicated by analysis of the 31 P NMR spectra, though they are unexpected P-O-P bridged compounds, of a type which has been synthesised previously by different methods. [27][28][29][30] The cyclophosphazene rings are essentially planar with the maximum deviations from the mean plane of 0.049 A ˚(P2) and 0.026 A ˚(N6) for compound 5b and 0.107 A ˚(N1), 0.042 A ˚(N7) for compound 5c. The two cyclophosphazene rings are bridged via O-atoms from the P(NHR) groups in which the P-O-P bond angles (138.7 for 5b and 137.2 for 5c) and average P-O bond lengths (1.602 A ˚for 5b and 1.603 A ˚for 5c) are similar to values for analogous P-O-P compounds in the literature [29][30][31] The P(NHR) side groups are arranged in an 'anti-parallel' manner with respect to each other with very similar conformations found for compounds 5b and 5c as shown by the superposition of their structures in Fig.…”