Transition-Metal Derivatives of Polyphosphazenes: Syntheses of Polyphosphazenes and Cyclic Model Compounds with Iron Cyclopentadienyl Carbonyl Side Groups

Harry R. Allcock, Michael N. Mang, Gayann S. Mcdonnell, Masood Parvez

Research output: Contribution to journalArticle

31 Citations (Scopus)

Abstract

The first high polymeric phosphazenes with skeletal phosphorus-transition-metal covalent bonds are reported. These species have been synthesized via two routes: (a) by the interaction of an organometallic iron anion, [FeCp(CO)2]~ with a mixed-substituent polyphosphazene bearing both chloro-and trifluoroethoxy side groups, and (b) by the reaction of an organometallic halide, FeCp(CO)2I, with a polyphosphazene that bears anionic sites at skeletal phosphorus. The polymers have been characterized by31P and 1H NMR and infrared spectroscopy, gel permeation chromatography, and thermal analyses. Spectroscopic comparisons are made with cyclic trimeric model molecules that bear the same substituent groups. The molecular structural characteristics of the polymers have also been probed indirectly by means of a single-crystal X-ray structure study of the small molecule model species, N3p3(OCH2CF3)5FeCp(CO)2. Crystals of N3P3(OCH2CF3)5FeCp(CO)2 are monoclinic and have the following parameters: space group P21/n, a = 9.690 (4) A, b = 20.684 (4) A, c - 15.082 (2) A, /? = 101.15 (2)°, V = 2965.8 A3, Z = 4.

Original languageEnglish (US)
Pages (from-to)2060-2067
Number of pages8
JournalMacromolecules
Volume20
Issue number9
DOIs
StatePublished - Sep 1 1987

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Organometallics
Carbon Monoxide
Transition metals
Phosphorus
Bearings (structural)
Iron
Derivatives
Molecules
Covalent bonds
Gel permeation chromatography
Polymers
Nuclear magnetic resonance spectroscopy
Infrared spectroscopy
Negative ions
Single crystals
X rays
Crystals
Anions
Hot Temperature
poly(phosphazene)

All Science Journal Classification (ASJC) codes

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

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abstract = "The first high polymeric phosphazenes with skeletal phosphorus-transition-metal covalent bonds are reported. These species have been synthesized via two routes: (a) by the interaction of an organometallic iron anion, [FeCp(CO)2]~ with a mixed-substituent polyphosphazene bearing both chloro-and trifluoroethoxy side groups, and (b) by the reaction of an organometallic halide, FeCp(CO)2I, with a polyphosphazene that bears anionic sites at skeletal phosphorus. The polymers have been characterized by31P and 1H NMR and infrared spectroscopy, gel permeation chromatography, and thermal analyses. Spectroscopic comparisons are made with cyclic trimeric model molecules that bear the same substituent groups. The molecular structural characteristics of the polymers have also been probed indirectly by means of a single-crystal X-ray structure study of the small molecule model species, N3p3(OCH2CF3)5FeCp(CO)2. Crystals of N3P3(OCH2CF3)5FeCp(CO)2 are monoclinic and have the following parameters: space group P21/n, a = 9.690 (4) A, b = 20.684 (4) A, c - 15.082 (2) A, /? = 101.15 (2)°, V = 2965.8 A3, Z = 4.",
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Transition-Metal Derivatives of Polyphosphazenes : Syntheses of Polyphosphazenes and Cyclic Model Compounds with Iron Cyclopentadienyl Carbonyl Side Groups. / Allcock, Harry R.; Mang, Michael N.; Mcdonnell, Gayann S.; Parvez, Masood.

In: Macromolecules, Vol. 20, No. 9, 01.09.1987, p. 2060-2067.

Research output: Contribution to journalArticle

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T1 - Transition-Metal Derivatives of Polyphosphazenes

T2 - Syntheses of Polyphosphazenes and Cyclic Model Compounds with Iron Cyclopentadienyl Carbonyl Side Groups

AU - Allcock, Harry R.

AU - Mang, Michael N.

AU - Mcdonnell, Gayann S.

AU - Parvez, Masood

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N2 - The first high polymeric phosphazenes with skeletal phosphorus-transition-metal covalent bonds are reported. These species have been synthesized via two routes: (a) by the interaction of an organometallic iron anion, [FeCp(CO)2]~ with a mixed-substituent polyphosphazene bearing both chloro-and trifluoroethoxy side groups, and (b) by the reaction of an organometallic halide, FeCp(CO)2I, with a polyphosphazene that bears anionic sites at skeletal phosphorus. The polymers have been characterized by31P and 1H NMR and infrared spectroscopy, gel permeation chromatography, and thermal analyses. Spectroscopic comparisons are made with cyclic trimeric model molecules that bear the same substituent groups. The molecular structural characteristics of the polymers have also been probed indirectly by means of a single-crystal X-ray structure study of the small molecule model species, N3p3(OCH2CF3)5FeCp(CO)2. Crystals of N3P3(OCH2CF3)5FeCp(CO)2 are monoclinic and have the following parameters: space group P21/n, a = 9.690 (4) A, b = 20.684 (4) A, c - 15.082 (2) A, /? = 101.15 (2)°, V = 2965.8 A3, Z = 4.

AB - The first high polymeric phosphazenes with skeletal phosphorus-transition-metal covalent bonds are reported. These species have been synthesized via two routes: (a) by the interaction of an organometallic iron anion, [FeCp(CO)2]~ with a mixed-substituent polyphosphazene bearing both chloro-and trifluoroethoxy side groups, and (b) by the reaction of an organometallic halide, FeCp(CO)2I, with a polyphosphazene that bears anionic sites at skeletal phosphorus. The polymers have been characterized by31P and 1H NMR and infrared spectroscopy, gel permeation chromatography, and thermal analyses. Spectroscopic comparisons are made with cyclic trimeric model molecules that bear the same substituent groups. The molecular structural characteristics of the polymers have also been probed indirectly by means of a single-crystal X-ray structure study of the small molecule model species, N3p3(OCH2CF3)5FeCp(CO)2. Crystals of N3P3(OCH2CF3)5FeCp(CO)2 are monoclinic and have the following parameters: space group P21/n, a = 9.690 (4) A, b = 20.684 (4) A, c - 15.082 (2) A, /? = 101.15 (2)°, V = 2965.8 A3, Z = 4.

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