Abstract
Exposure of the following cyclic phosphazenes to 60Co γ-rays at 77 K gives electron-gain centres having e.s.r. spectra characteristic of phosphoranyl radicals: N3P3X6(X = Cl or Br), N3P3Cl3(NMe2)3 and N4P4X8(X = Cl or Br). This means that, rather than accommodating the extra electron in a delocalised π orbital of a pseudo-aromatic type, the radical anion distorts so that the electron is confined to a single phosphorus atom having a local trigonal-bipyramidal configuration, with the orbital of the unpaired electron on phosphorus directed radially away from the ring.
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