Reactivity and Polymerization Behavior of a Pentachlorocyclocarbophosphazene, N3P2CCl5

Harry R. Allcock, Suzanne M. Coley, Ian Manners, Karyn B. Visscher, Masood Parvez, Oskar Nuyken, Gerhard Renner

Research output: Contribution to journalArticle

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Abstract

The cyclic carbophosphazene N3P2CCl5 reacts with sodium methoxide, sodium trifluoroethoxide, and sodium phenoxide to yield the corresponding pentaalkoxy- and pentakis(aryloxy)cyclocarbophosphazenes. By contrast, N3P2CCl5 does not react with the main group and transition metal nucleophiles lithium diphenylphosphide and lithium pentacarbonylmanganate and reacts incompletely with sodium dicarbonyl(η5-2,4-cyclopentadien-1-yl)ferrate. The title compound undergoes thermal ring-opening polymerization when heated to 120°C. This polymerization was monitored by 31P NMR spectroscopy. Aspects of the mechanism of polymerization are discussed. Crystal structures of N3P2CCl5 and N3P2C(OPh)5 were obtained by X-ray diffraction. The crystals of N3P2CCl5 are orthorhombic, of space group Pbca, with a = 7.7880 Å, b = 29.3560 Å, c = 16.7990 Å, β = 90.00°, V = 3840 Å3, and Z = 16, whereas crystals of N3P2C(OC6H5)5 are triclinic, of space group P1̄, with a = 10.249(2) Å, b = 12.290(4) Å, c = 14.437(2) Å, α = 84.65(2)°, β = 85.57(1)°, γ = 70.82(2)°, V = 1708.08 Å3, and Z = 2.

Original languageEnglish (US)
Pages (from-to)5088-5094
Number of pages7
JournalInorganic Chemistry
Volume32
Issue number23
DOIs
StatePublished - Jan 1 1993

Fingerprint

polymerization
reactivity
Sodium
Polymerization
sodium
Crystals
Nucleophiles
lithium
Ring opening polymerization
ferrates
Lithium
Nuclear magnetic resonance spectroscopy
Transition metals
Methanol
nucleophiles
Crystal structure
crystals
X ray diffraction
transition metals
nuclear magnetic resonance

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Allcock, H. R., Coley, S. M., Manners, I., Visscher, K. B., Parvez, M., Nuyken, O., & Renner, G. (1993). Reactivity and Polymerization Behavior of a Pentachlorocyclocarbophosphazene, N3P2CCl5. Inorganic Chemistry, 32(23), 5088-5094. https://doi.org/10.1021/ic00075a024
Allcock, Harry R. ; Coley, Suzanne M. ; Manners, Ian ; Visscher, Karyn B. ; Parvez, Masood ; Nuyken, Oskar ; Renner, Gerhard. / Reactivity and Polymerization Behavior of a Pentachlorocyclocarbophosphazene, N3P2CCl5. In: Inorganic Chemistry. 1993 ; Vol. 32, No. 23. pp. 5088-5094.
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title = "Reactivity and Polymerization Behavior of a Pentachlorocyclocarbophosphazene, N3P2CCl5",
abstract = "The cyclic carbophosphazene N3P2CCl5 reacts with sodium methoxide, sodium trifluoroethoxide, and sodium phenoxide to yield the corresponding pentaalkoxy- and pentakis(aryloxy)cyclocarbophosphazenes. By contrast, N3P2CCl5 does not react with the main group and transition metal nucleophiles lithium diphenylphosphide and lithium pentacarbonylmanganate and reacts incompletely with sodium dicarbonyl(η5-2,4-cyclopentadien-1-yl)ferrate. The title compound undergoes thermal ring-opening polymerization when heated to 120°C. This polymerization was monitored by 31P NMR spectroscopy. Aspects of the mechanism of polymerization are discussed. Crystal structures of N3P2CCl5 and N3P2C(OPh)5 were obtained by X-ray diffraction. The crystals of N3P2CCl5 are orthorhombic, of space group Pbca, with a = 7.7880 {\AA}, b = 29.3560 {\AA}, c = 16.7990 {\AA}, β = 90.00°, V = 3840 {\AA}3, and Z = 16, whereas crystals of N3P2C(OC6H5)5 are triclinic, of space group P1̄, with a = 10.249(2) {\AA}, b = 12.290(4) {\AA}, c = 14.437(2) {\AA}, α = 84.65(2)°, β = 85.57(1)°, γ = 70.82(2)°, V = 1708.08 {\AA}3, and Z = 2.",
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Allcock, HR, Coley, SM, Manners, I, Visscher, KB, Parvez, M, Nuyken, O & Renner, G 1993, 'Reactivity and Polymerization Behavior of a Pentachlorocyclocarbophosphazene, N3P2CCl5', Inorganic Chemistry, vol. 32, no. 23, pp. 5088-5094. https://doi.org/10.1021/ic00075a024

Reactivity and Polymerization Behavior of a Pentachlorocyclocarbophosphazene, N3P2CCl5. / Allcock, Harry R.; Coley, Suzanne M.; Manners, Ian; Visscher, Karyn B.; Parvez, Masood; Nuyken, Oskar; Renner, Gerhard.

In: Inorganic Chemistry, Vol. 32, No. 23, 01.01.1993, p. 5088-5094.

Research output: Contribution to journalArticle

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T1 - Reactivity and Polymerization Behavior of a Pentachlorocyclocarbophosphazene, N3P2CCl5

AU - Allcock, Harry R.

AU - Coley, Suzanne M.

AU - Manners, Ian

AU - Visscher, Karyn B.

AU - Parvez, Masood

AU - Nuyken, Oskar

AU - Renner, Gerhard

PY - 1993/1/1

Y1 - 1993/1/1

N2 - The cyclic carbophosphazene N3P2CCl5 reacts with sodium methoxide, sodium trifluoroethoxide, and sodium phenoxide to yield the corresponding pentaalkoxy- and pentakis(aryloxy)cyclocarbophosphazenes. By contrast, N3P2CCl5 does not react with the main group and transition metal nucleophiles lithium diphenylphosphide and lithium pentacarbonylmanganate and reacts incompletely with sodium dicarbonyl(η5-2,4-cyclopentadien-1-yl)ferrate. The title compound undergoes thermal ring-opening polymerization when heated to 120°C. This polymerization was monitored by 31P NMR spectroscopy. Aspects of the mechanism of polymerization are discussed. Crystal structures of N3P2CCl5 and N3P2C(OPh)5 were obtained by X-ray diffraction. The crystals of N3P2CCl5 are orthorhombic, of space group Pbca, with a = 7.7880 Å, b = 29.3560 Å, c = 16.7990 Å, β = 90.00°, V = 3840 Å3, and Z = 16, whereas crystals of N3P2C(OC6H5)5 are triclinic, of space group P1̄, with a = 10.249(2) Å, b = 12.290(4) Å, c = 14.437(2) Å, α = 84.65(2)°, β = 85.57(1)°, γ = 70.82(2)°, V = 1708.08 Å3, and Z = 2.

AB - The cyclic carbophosphazene N3P2CCl5 reacts with sodium methoxide, sodium trifluoroethoxide, and sodium phenoxide to yield the corresponding pentaalkoxy- and pentakis(aryloxy)cyclocarbophosphazenes. By contrast, N3P2CCl5 does not react with the main group and transition metal nucleophiles lithium diphenylphosphide and lithium pentacarbonylmanganate and reacts incompletely with sodium dicarbonyl(η5-2,4-cyclopentadien-1-yl)ferrate. The title compound undergoes thermal ring-opening polymerization when heated to 120°C. This polymerization was monitored by 31P NMR spectroscopy. Aspects of the mechanism of polymerization are discussed. Crystal structures of N3P2CCl5 and N3P2C(OPh)5 were obtained by X-ray diffraction. The crystals of N3P2CCl5 are orthorhombic, of space group Pbca, with a = 7.7880 Å, b = 29.3560 Å, c = 16.7990 Å, β = 90.00°, V = 3840 Å3, and Z = 16, whereas crystals of N3P2C(OC6H5)5 are triclinic, of space group P1̄, with a = 10.249(2) Å, b = 12.290(4) Å, c = 14.437(2) Å, α = 84.65(2)°, β = 85.57(1)°, γ = 70.82(2)°, V = 1708.08 Å3, and Z = 2.

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