Reactions of Bi(cyclophosphazenes) with Sodium Alkoxides or Aryl Oxides

Harry R. Allcock, Mark S. Connolly, Paul J. Harris

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14 Scopus citations

Abstract

Bi(cyclophosphazenes) (2) react with nucleophiles such as sodium trifluoroethoxide or sodium phenoxide by two alternative pathways—(a) with cleavage of the PP ring linkage unit and cleavage of PCl bonds to yield organocyclotriphosphazenes (3) or (b) by cleavage of PCl bonds without rupture of PP bonds to give organobi(cyclophosphazenes) (6). These latter species eventually undergo PP bond scission with alkoxides or aryl oxides under more forcing reaction conditions. Cleavage of the bi(cyclophosphazenes) 2 or 6 also yields phosphazene anions (4), which react with alcohols to form hydridocyclotriphosphazenes (5). Treatment of these with chlorine brings about the conversion of the PH to PCl units. The phosphazene anions (4) also react with allyl bromide with attachment of the allyl residue to the ring and with carbon tetrachloride to abstract Cl+ and generate neutral chloroorganocyclotriphosphazene species (9). These interconnected processes were monitored by both product isolation and NMR spectroscopy. Appendices A and B (supplementary material) outline the interpretation of the more complex 1H and 31P NMR coupling patterns observed.

Original languageEnglish (US)
Pages (from-to)2482-2490
Number of pages9
JournalJournal of the American Chemical Society
Volume104
Issue number9
DOIs
StatePublished - 1982

All Science Journal Classification (ASJC) codes

  • Catalysis
  • General Chemistry
  • Biochemistry
  • Colloid and Surface Chemistry

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