Cyanophosphazene Small Molecules and High Polymers: Synthesis and Structure

Harry R. Allcock, J. Steven Rutt, Mark F. Welker, Masood Parvez

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Abstract

The synthesis and properties of cyclic and high-polymeric cyanophosphazenes were investigated. The interaction of N3P3(OR)5Cl (OR = OC6H5, OCH2CF3, OCH2CH2OCH2CH2OCH3) with potassium cyanide in the presence of 18-crown-6 ether in acetonitrile yielded small-molecule cyclic cyanophosphazenes, N3P3(OR)5(CN). Reaction of trans-nongeminal-[NP(NMe2)Cl]3 with potassium cyanide in the presence of tetra-n-butylammonium bromide in acetonitrile resulted in the formation of trans-nongeminal-[NP(NMe2)(CN)]3. X-ray crystallographic analyses of N3P3(OC6H5)5(CN) and nongeminal-[NP(NMe2)(CN)]3 were carried out. N3P3(OC6H5)5(CN) crystallized in the monoclinic space group P21/n. Unit cell parameters were a = 10.759(4) Å, b = 9.662(3) Å, c = 29.466(4) Å, and β = 96.92(3)°. The structure refined with final R = 0.045 and Rw = 0.047. nongeminal-[NP(NMe2)(CN)]3 crystallized in the triclinic space group P1¯. Unit cell parameters were a = 6.715(3) Å, b = 8.538(5) Å, c = 14.910(6) Å, α = 92.10(4)°, β = 105.41(4)°, and γ = 95.75(4)°. The structure refined to a final R = 0.044 and Rw., = 0.061. The syntheses of high-polymeric cyanophosphazenes were carried out by the reaction of [NPR1.5.Cl0.5]n, (R = OC6H5 or NMe2) with potassium cyanide in the presence of 18-crown-6 ether in THF to yield [NP(OC6H5),1.53(CN)0.33 Cl0.14]n and [NP(NMe2)1.5(CN)0.3Cl0.2]n· Attempts to replace the remaining chlorine atoms in [NP(OC6H5)1.5(CN)0.33 Cl0.17]n by reaction with NaOC6H5 resulted in the displacement of both chloro and cyano units to give [NP(OC6H5)2]n. Treatment of [NP(NMe2)1.5(CN)0.3Cl0.2]n with excess HNMe2 gave [NP(NMe2)1.7(CN)0.3]n. The polymers were studied by a combination of NMR, IR, DSC, GPC, TGA, and elemental analysis.

Original languageEnglish (US)
Pages (from-to)2315-2321
Number of pages7
JournalInorganic Chemistry
Volume32
Issue number11
DOIs
StatePublished - Jan 1 1993

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All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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