ic801536z_si_002.cif (15.96 kB)

Experimental and Theoretical Characterization of the Hexaazidophosphate(V) Ion

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posted on 15.12.2008, 00:00 by P. Portius, P. W. Fowler, H. Adams, T. Z. Todorova
(PPN)[P(N3)6] (2) was synthesized by the metathesis of Na[P(N3)6] (1) and (PPN)N3 (PPN+ = {(Ph3P)2N}+), allowing for the isolation and full characterization of a stable hexaazidophosphate(V) salt by 31P and 14N NMR, UV absorption, IR and Raman spectroscopy, elemental and thermal analyses, X-ray diffraction, and Hartree−Fock and density functional theory calculations. The colorless single crystals of 2 are triclinic, space group P1̅, a = 9.6296(9), b = 9.8158(9), c = 10.1414(10) Å, α = 92.635(5)°, β = 93.437(5)°, γ = 92.105(4)°, and Z = 1. The [P(N3)6] ion of 2 is isolated in the solid state and adopts S6 symmetry both in the crystal and in solution. Thermogravimetric analysis and differential scanning calorimetry measurements reveal a surprising thermal stability of 2 (Tdec ca. 200 °C). No friction sensitivity was encountered.