Synthesis and Characterization of Metallophosphazene Derivatives: Solution State and Surface Reactions

Harry R. Allcock, Eric N. Silverberg, Constance J. Nelson, William D. Coggio

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15 Scopus citations


The small-molecule cyclotriphosphazenes N3P3(OPh)5OC6H4R and N3P3(OC6H4R)6 where R = FeCp(CO)2 were synthesized by reaction of the corresponding [(lithioaryl)oxy]phosphazenes with cyclopentadienyliron dicarbonyl iodide in the absence of moisture, oxygen, and light. Molecular structural characterization for the cyclic trimers was achieved by 1H, 13C., and 31P NMR spectroscopy, infrared spectroscopy, elemental microanalysis, and FAB mass spectrometry. These small-molecule reactions were used as models for the preparation of the corresponding high polymeric analogues. The synthesis of the poly(metallophosphazene), tNP(OC6H4R)x-(OC6H4X)2−x]n, where X = H or Br and R = FeCp(CO)2, via the metal-halogen exchange reaction of [NP(OC6H4Br)2]n with n-BuLi at −78 °C., is described. Structural characterization for this polymer was carried out by solid-state 13C NMR spectroscopy, KBr infrared spectroscopy, and elemental microanalysis. Thermal properties were investigated via differential scanning calorimetry, thermogravimetric analysis (TGA), and TGA/mass spectrometry. The organometallic-containing polymers showed solid-state paramagnetic behavior. Modification reactions at the surface interfacial region of cross-linked films of [NP(OC6H4Br)2]n were also investigated. Controlled exposure of these films to lithiation and metal-halogen exchange conditions, as described above, allowed the preparation of surface-metalated materials. These surface-metalated films were characterized by the use of X-ray microanalysis and scanning electron microscopy (SEM), transmission electron microscopy (TEM), contact angle measurements, and attenuated transmission reflectance infrared spectroscopy (ATR-IR).

Original languageEnglish (US)
Pages (from-to)1307-1314
Number of pages8
JournalChemistry of Materials
Issue number9
StatePublished - 1993

All Science Journal Classification (ASJC) codes

  • General Chemistry
  • General Chemical Engineering
  • Materials Chemistry


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