Chemistry of polyfunctional molecules - 123.1 reactions of BiBr3, SbI3 and AsI3 with LiN(PPh2)2; X-ray structure of a cyclophosphazene salt containing arsenic(I)

Article abstract of DOI:10.1016/0277-5387(96)00200-8

BiBr₃ or SbI₃ react at 20°C with LiN(PPh₂)₂ (1) to give elementary Bi or Sb and the P-P coupled phosphazene ligand Ph₂P-N=PPh₂-PPh₂=N-PPh₂ (2). The reaction of AsI₃ with 1 at room temperature formed yellow needles of the eight-membered heterocycle AsPPh₂NPPh₂AsPPh₂NPPh₂ (3), whereas AsI₃ interacted at 80°C with 1 in the molar ratio of 1:3 to give elementary arsenic and 2. Treatment of AsI₃ and 1 at 20°C in a 1:2 stoichiometry yielded the seven-membered, cyclic arsenium (I) salt [As_-...PPh₂-N=PPh₂-PPh₂=N-PPh ₂] I · 4THF (5 · 4THF), which was characterized by elemental analysis, conductivity, mass, IR and NMR spectroscopy and single-crystal X-ray structural analysis. Copyright