TY - JOUR
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
N1 - Copyright:
Copyright 2017 Elsevier B.V., All rights reserved.
PY - 1993
Y1 - 1993
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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U2 - 10.1021/ic00075a024
DO - 10.1021/ic00075a024
M3 - Article
AN - SCOPUS:0042396888
SN - 0020-1669
VL - 32
SP - 5088
EP - 5094
JO - Inorganic chemistry
JF - Inorganic chemistry
IS - 23
ER -