Cyanophosphazene Small Molecules and High Polymers: Synthesis and Structure

H. R. Allcock; J. Steven Rutt; Mark F. Welker; Masood Parvez

doi:10.1021/ic00063a021

Cyanophosphazene Small Molecules and High Polymers: Synthesis and Structure

H. 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 R_w = 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 R_w., = 0.061. The syntheses of high-polymeric cyanophosphazenes were carried out by the reaction of [NPR_1.5.Cl_0.5]_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⁻ Cl_0.14]_n and [NP(NMe₂)_1.5(CN)_0.3Cl_0.2]_n· Attempts to replace the remaining chlorine atoms in [NP(OC₆H₅)_1.5(CN)_0.33⁻ Cl_0.17]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)_0.3Cl_0.2]_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 language	English (US)
Pages (from-to)	2315-2321
Number of pages	7
Journal	Inorganic chemistry
Volume	32
Issue number	11
DOIs	https://doi.org/10.1021/ic00063a021
State	Published - 1993

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Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/ic00063a021

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@article{c4e5095fa8ae4760bdc131497e7591de,

title = "Cyanophosphazene Small Molecules and High Polymers: Synthesis and Structure",

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) {\AA}, b = 9.662(3) {\AA}, c = 29.466(4) {\AA}, 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) {\AA}, b = 8.538(5) {\AA}, c = 14.910(6) {\AA}, 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.",

author = "Allcock, {H. R.} and Rutt, {J. Steven} and Welker, {Mark F.} and Masood Parvez",

year = "1993",

doi = "10.1021/ic00063a021",

language = "English (US)",

volume = "32",

pages = "2315--2321",

journal = "Inorganic chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "11",

}

TY - JOUR

T1 - Cyanophosphazene Small Molecules and High Polymers

T2 - Synthesis and Structure

AU - Allcock, H. R.

AU - Rutt, J. Steven

AU - Welker, Mark F.

AU - Parvez, Masood

PY - 1993

Y1 - 1993

N2 - 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.

AB - 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.

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UR - http://www.scopus.com/inward/citedby.url?scp=4243405178&partnerID=8YFLogxK

U2 - 10.1021/ic00063a021

DO - 10.1021/ic00063a021

M3 - Article

AN - SCOPUS:4243405178

SN - 0020-1669

VL - 32

SP - 2315

EP - 2321

JO - Inorganic chemistry

JF - Inorganic chemistry

IS - 11

ER -

Cyanophosphazene Small Molecules and High Polymers: Synthesis and Structure

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