Organometallic Phosphazenes: Synthesis and Rearrangement of Propynyl- and Propadienylcyclotriphosphazenes

Harry R. Allcock, P. J. Harris, R. A. Nissan

Research output: Contribution to journalArticle

42 Citations (Scopus)

Abstract

A new series of 1,1-dialkyltetrachlorocyclotriphosphazenes with prop-2-ynyl (VI), prop-l,2-dienyl (V), and prop-l-ynyl (XII) substituents have been prepared. These syntheses involve the reactions of cuprio- or lithiophosphazene anions (II or IX) with prop-2-ynyl bromide which lead initially to the formation of the prop-2-ynyl complexes (VI). The prop-2-ynyl side group was found to undergo an alumina-initiated rearrangement to the prop-l,2-dienyl group (V), and both compounds VI and V underwent a methyllithium-initiated rearrangement to the prop-l-ynyl derivatives (XII). These organometallic-initiated rearrangements were monitored by 31P NMR spectroscopy. The structural characterization of all the new compounds is described, and the NMR results, together with the various rearrangements, are discussed in terms of electronic interactions between the C3H3 group and the phosphazene ring. The formation of the lithiophosphazene anion (IX, R = CH3) was studied by low-temperature 31P NMR spectroscopy, and the results are discussed in terms of the electron distribution within the phosphazene ring.

Original languageEnglish (US)
Pages (from-to)2256-2261
Number of pages6
JournalJournal of the American Chemical Society
Volume103
Issue number9
DOIs
StatePublished - Jan 1 1981

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Organometallics
Nuclear magnetic resonance spectroscopy
Anions
Magnetic Resonance Spectroscopy
Negative ions
Aluminum Oxide
Bromides
Alumina
Nuclear magnetic resonance
Electrons
Derivatives
Temperature
methyllithium
lead bromide

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

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title = "Organometallic Phosphazenes: Synthesis and Rearrangement of Propynyl- and Propadienylcyclotriphosphazenes",
abstract = "A new series of 1,1-dialkyltetrachlorocyclotriphosphazenes with prop-2-ynyl (VI), prop-l,2-dienyl (V), and prop-l-ynyl (XII) substituents have been prepared. These syntheses involve the reactions of cuprio- or lithiophosphazene anions (II or IX) with prop-2-ynyl bromide which lead initially to the formation of the prop-2-ynyl complexes (VI). The prop-2-ynyl side group was found to undergo an alumina-initiated rearrangement to the prop-l,2-dienyl group (V), and both compounds VI and V underwent a methyllithium-initiated rearrangement to the prop-l-ynyl derivatives (XII). These organometallic-initiated rearrangements were monitored by 31P NMR spectroscopy. The structural characterization of all the new compounds is described, and the NMR results, together with the various rearrangements, are discussed in terms of electronic interactions between the C3H3 group and the phosphazene ring. The formation of the lithiophosphazene anion (IX, R = CH3) was studied by low-temperature 31P NMR spectroscopy, and the results are discussed in terms of the electron distribution within the phosphazene ring.",
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Organometallic Phosphazenes : Synthesis and Rearrangement of Propynyl- and Propadienylcyclotriphosphazenes. / Allcock, Harry R.; Harris, P. J.; Nissan, R. A.

In: Journal of the American Chemical Society, Vol. 103, No. 9, 01.01.1981, p. 2256-2261.

Research output: Contribution to journalArticle

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AB - A new series of 1,1-dialkyltetrachlorocyclotriphosphazenes with prop-2-ynyl (VI), prop-l,2-dienyl (V), and prop-l-ynyl (XII) substituents have been prepared. These syntheses involve the reactions of cuprio- or lithiophosphazene anions (II or IX) with prop-2-ynyl bromide which lead initially to the formation of the prop-2-ynyl complexes (VI). The prop-2-ynyl side group was found to undergo an alumina-initiated rearrangement to the prop-l,2-dienyl group (V), and both compounds VI and V underwent a methyllithium-initiated rearrangement to the prop-l-ynyl derivatives (XII). These organometallic-initiated rearrangements were monitored by 31P NMR spectroscopy. The structural characterization of all the new compounds is described, and the NMR results, together with the various rearrangements, are discussed in terms of electronic interactions between the C3H3 group and the phosphazene ring. The formation of the lithiophosphazene anion (IX, R = CH3) was studied by low-temperature 31P NMR spectroscopy, and the results are discussed in terms of the electron distribution within the phosphazene ring.

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