Cyclotriphosphazenes with Geminal (Trimethylsilyl)methyl and Alkyl or Aryl Side Groups

Harry R. Allcock, David J. Brennan, Beverly S. Dunn, Masood Parvez

Research output: Contribution to journalArticle

17 Citations (Scopus)

Abstract

The synthesis of a series of organosilyl cyclophosphazenes of formula gem-N3P3Cl4(CH2SiMe3)(R), where R = C2H5, i-C3H7, n-C4H9, t-C4H9, neo-C5H11, and C6H5, via organometallic reactions, is described. The chlorine atoms in the cyclic trimers were replaced by trifluoroethoxy groups by reactions that led to either retention of the (trimethylsilyl)methyl units or replacement of them by methyl groups, depending on the reaction conditions. The crystal and molecular structures of gem-N3P3Cl4-(CH2SiMe3)(t-C4H9) and the related derivative gem-N3P3Cl4(CH2SiMe3)2 were determined by single-crystal X-ray diffraction methods. Steric hindrance involving the organosilyl units results in a widening of the external angle at the supporting phosphorus atom and a narrowing of the corresponding ring angle at that site. Crystals of gem-N3P3Cl4(CH2SiMe3)(t-C4H9) are orthorhombic with space group Pbca, with a = 14.884 (4) Å, b = 15.815 (4) Å, c = 16.615 (4) Å, V = 3910.9 Å3, and Z = 8. Crystals of gem-N3P3Cl4(CH2SiMe3)2 are monoclinic with space group P21/n, with a = 10.145 (4) Å, b = 11.060 (5) Å, c = 19.999 (6) Å, β = 103.56 (3)°, V = 2181.4 Å3, and Z = 4.

Original languageEnglish (US)
Pages (from-to)3226-3233
Number of pages8
JournalInorganic Chemistry
Volume27
Issue number18
DOIs
StatePublished - Sep 1 1988

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Gems
trimers
Atoms
Crystals
crystals
Chlorine
chlorine
atoms
phosphorus
Organometallics
molecular structure
Phosphorus
Molecular structure
Crystal structure
crystal structure
Single crystals
rings
single crystals
Derivatives
synthesis

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Allcock, Harry R. ; Brennan, David J. ; Dunn, Beverly S. ; Parvez, Masood. / Cyclotriphosphazenes with Geminal (Trimethylsilyl)methyl and Alkyl or Aryl Side Groups. In: Inorganic Chemistry. 1988 ; Vol. 27, No. 18. pp. 3226-3233.
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title = "Cyclotriphosphazenes with Geminal (Trimethylsilyl)methyl and Alkyl or Aryl Side Groups",
abstract = "The synthesis of a series of organosilyl cyclophosphazenes of formula gem-N3P3Cl4(CH2SiMe3)(R), where R = C2H5, i-C3H7, n-C4H9, t-C4H9, neo-C5H11, and C6H5, via organometallic reactions, is described. The chlorine atoms in the cyclic trimers were replaced by trifluoroethoxy groups by reactions that led to either retention of the (trimethylsilyl)methyl units or replacement of them by methyl groups, depending on the reaction conditions. The crystal and molecular structures of gem-N3P3Cl4-(CH2SiMe3)(t-C4H9) and the related derivative gem-N3P3Cl4(CH2SiMe3)2 were determined by single-crystal X-ray diffraction methods. Steric hindrance involving the organosilyl units results in a widening of the external angle at the supporting phosphorus atom and a narrowing of the corresponding ring angle at that site. Crystals of gem-N3P3Cl4(CH2SiMe3)(t-C4H9) are orthorhombic with space group Pbca, with a = 14.884 (4) {\AA}, b = 15.815 (4) {\AA}, c = 16.615 (4) {\AA}, V = 3910.9 {\AA}3, and Z = 8. Crystals of gem-N3P3Cl4(CH2SiMe3)2 are monoclinic with space group P21/n, with a = 10.145 (4) {\AA}, b = 11.060 (5) {\AA}, c = 19.999 (6) {\AA}, β = 103.56 (3)°, V = 2181.4 {\AA}3, and Z = 4.",
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Cyclotriphosphazenes with Geminal (Trimethylsilyl)methyl and Alkyl or Aryl Side Groups. / Allcock, Harry R.; Brennan, David J.; Dunn, Beverly S.; Parvez, Masood.

In: Inorganic Chemistry, Vol. 27, No. 18, 01.09.1988, p. 3226-3233.

Research output: Contribution to journalArticle

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T1 - Cyclotriphosphazenes with Geminal (Trimethylsilyl)methyl and Alkyl or Aryl Side Groups

AU - Allcock, Harry R.

AU - Brennan, David J.

AU - Dunn, Beverly S.

AU - Parvez, Masood

PY - 1988/9/1

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N2 - The synthesis of a series of organosilyl cyclophosphazenes of formula gem-N3P3Cl4(CH2SiMe3)(R), where R = C2H5, i-C3H7, n-C4H9, t-C4H9, neo-C5H11, and C6H5, via organometallic reactions, is described. The chlorine atoms in the cyclic trimers were replaced by trifluoroethoxy groups by reactions that led to either retention of the (trimethylsilyl)methyl units or replacement of them by methyl groups, depending on the reaction conditions. The crystal and molecular structures of gem-N3P3Cl4-(CH2SiMe3)(t-C4H9) and the related derivative gem-N3P3Cl4(CH2SiMe3)2 were determined by single-crystal X-ray diffraction methods. Steric hindrance involving the organosilyl units results in a widening of the external angle at the supporting phosphorus atom and a narrowing of the corresponding ring angle at that site. Crystals of gem-N3P3Cl4(CH2SiMe3)(t-C4H9) are orthorhombic with space group Pbca, with a = 14.884 (4) Å, b = 15.815 (4) Å, c = 16.615 (4) Å, V = 3910.9 Å3, and Z = 8. Crystals of gem-N3P3Cl4(CH2SiMe3)2 are monoclinic with space group P21/n, with a = 10.145 (4) Å, b = 11.060 (5) Å, c = 19.999 (6) Å, β = 103.56 (3)°, V = 2181.4 Å3, and Z = 4.

AB - The synthesis of a series of organosilyl cyclophosphazenes of formula gem-N3P3Cl4(CH2SiMe3)(R), where R = C2H5, i-C3H7, n-C4H9, t-C4H9, neo-C5H11, and C6H5, via organometallic reactions, is described. The chlorine atoms in the cyclic trimers were replaced by trifluoroethoxy groups by reactions that led to either retention of the (trimethylsilyl)methyl units or replacement of them by methyl groups, depending on the reaction conditions. The crystal and molecular structures of gem-N3P3Cl4-(CH2SiMe3)(t-C4H9) and the related derivative gem-N3P3Cl4(CH2SiMe3)2 were determined by single-crystal X-ray diffraction methods. Steric hindrance involving the organosilyl units results in a widening of the external angle at the supporting phosphorus atom and a narrowing of the corresponding ring angle at that site. Crystals of gem-N3P3Cl4(CH2SiMe3)(t-C4H9) are orthorhombic with space group Pbca, with a = 14.884 (4) Å, b = 15.815 (4) Å, c = 16.615 (4) Å, V = 3910.9 Å3, and Z = 8. Crystals of gem-N3P3Cl4(CH2SiMe3)2 are monoclinic with space group P21/n, with a = 10.145 (4) Å, b = 11.060 (5) Å, c = 19.999 (6) Å, β = 103.56 (3)°, V = 2181.4 Å3, and Z = 4.

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