Reaction of Sodium 2,2,2-Trifluoroethoxide with Hexachlorocyclotriphosphazene

J. L. Schmutz; H. R. Allcock

doi:10.1021/ic50152a027

Reaction of Sodium 2,2,2-Trifluoroethoxide with Hexachlorocyclotriphosphazene

J. L. Schmutz, H. R. Allcock

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Abstract

The reaction between sodium 2,2,2-trifluoroethoxide and hexachlorocyclotriphosphazene (I) yielded nine cyclotriphosphazenes of the formula N₃P₃(OCH₂CF₃)_nCl_6-n where = 1-6. Nuclear magnetic resonance analysis indicated that these products were compounds II-X. This constitutes the first isolation and identification of a complete series of alkoxychlorocyclophosphazenes. The reaction was found to follow almost exclusively a trans-nongeminal pathway, and a steric rather than an electronic “cis effect” is postulated to account for this pattern. Dipole moments were measured, but these were shown to be unsuitable for isomer identification, presumably because of the presence of the bulky, nonrigid trifluoroethoxy groups and a nonvanishing ring moment. The applicability of these results to related high molecular weight polyphosphazene systems is discussed.

Original language	English (US)
Pages (from-to)	2433-2438
Number of pages	6
Journal	Inorganic chemistry
Volume	14
Issue number	10
DOIs	https://doi.org/10.1021/ic50152a027
State	Published - Oct 1 1975

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Inorganic Chemistry

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title = "Reaction of Sodium 2,2,2-Trifluoroethoxide with Hexachlorocyclotriphosphazene",

abstract = "The reaction between sodium 2,2,2-trifluoroethoxide and hexachlorocyclotriphosphazene (I) yielded nine cyclotriphosphazenes of the formula N3P3(OCH2CF3)nCl6-n where = 1-6. Nuclear magnetic resonance analysis indicated that these products were compounds II-X. This constitutes the first isolation and identification of a complete series of alkoxychlorocyclophosphazenes. The reaction was found to follow almost exclusively a trans-nongeminal pathway, and a steric rather than an electronic “cis effect” is postulated to account for this pattern. Dipole moments were measured, but these were shown to be unsuitable for isomer identification, presumably because of the presence of the bulky, nonrigid trifluoroethoxy groups and a nonvanishing ring moment. The applicability of these results to related high molecular weight polyphosphazene systems is discussed.",

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T1 - Reaction of Sodium 2,2,2-Trifluoroethoxide with Hexachlorocyclotriphosphazene

AU - Schmutz, J. L.

AU - Allcock, H. R.

PY - 1975/10/1

Y1 - 1975/10/1

N2 - The reaction between sodium 2,2,2-trifluoroethoxide and hexachlorocyclotriphosphazene (I) yielded nine cyclotriphosphazenes of the formula N3P3(OCH2CF3)nCl6-n where = 1-6. Nuclear magnetic resonance analysis indicated that these products were compounds II-X. This constitutes the first isolation and identification of a complete series of alkoxychlorocyclophosphazenes. The reaction was found to follow almost exclusively a trans-nongeminal pathway, and a steric rather than an electronic “cis effect” is postulated to account for this pattern. Dipole moments were measured, but these were shown to be unsuitable for isomer identification, presumably because of the presence of the bulky, nonrigid trifluoroethoxy groups and a nonvanishing ring moment. The applicability of these results to related high molecular weight polyphosphazene systems is discussed.

AB - The reaction between sodium 2,2,2-trifluoroethoxide and hexachlorocyclotriphosphazene (I) yielded nine cyclotriphosphazenes of the formula N3P3(OCH2CF3)nCl6-n where = 1-6. Nuclear magnetic resonance analysis indicated that these products were compounds II-X. This constitutes the first isolation and identification of a complete series of alkoxychlorocyclophosphazenes. The reaction was found to follow almost exclusively a trans-nongeminal pathway, and a steric rather than an electronic “cis effect” is postulated to account for this pattern. Dipole moments were measured, but these were shown to be unsuitable for isomer identification, presumably because of the presence of the bulky, nonrigid trifluoroethoxy groups and a nonvanishing ring moment. The applicability of these results to related high molecular weight polyphosphazene systems is discussed.

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Reaction of Sodium 2,2,2-Trifluoroethoxide with Hexachlorocyclotriphosphazene

Abstract

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