Analysis and calculation of the 31P and 19F NMR spectra of hexafluorocyclotriphosphazene.

The higher order high-resolution 31P and 19F NMR spectra of hexafluorocyclotriphosphazene (F2PN)3 were measured at 183 K and interpreted using subspectral analysis and iterative fitting computation. (F2PN)3 forms a rigid nine-spin system [A[X]2]3 with D3h symmetry. Two complete and very similar sets of six experimental spin–spin coupling constants, 1J(P,F), 2J(P,P), 2J(F,F), 3J(P,F), 4J(F,F)cis and 4J(F,F)trans, were determined for the first time. Theoretical DFT calculations of chemical shifts and coupling constants were performed to assess their predictive value. The PP/aug-cc-pVDZ treatment rendered the best agreement with experimental data. Copyright © 2005 John Wiley & Sons, Ltd.