New Cyclic Phosphazenes with (Trimethylsilyl)methyl Side Groups: X-ray Crystal Structure of [NP(CH2SiMe3)2]3 and Its Conversion to (NPMe2)3

Harry R. Allcock; William D. Coggio; Masood Parvez; Michael L. Turner

doi:10.1021/om00049a029

New Cyclic Phosphazenes with (Trimethylsilyl)methyl Side Groups: X-ray Crystal Structure of [NP(CH₂SiMe₃)₂]₃ and Its Conversion to (NPMe₂)₃

Harry R. Allcock, William D. Coggio, Masood Parvez, Michael L. Turner

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Abstract

The synthesis of [NP(CH₂SiMe₃)₂]₃ has been achieved in almost quantitative yield via the reaction of Me₃SiCH₂Li with (NPF₂)₃ in tetrahydrofuran at 40 °C, followed by addition of a proton source. Treatment of [NP(CH₂SiMe₃)₂]₃ with ⁿBu₄N⁺F⁻ gave (NPMe₂)₃ in 60% yield. Partially substituted trimers of the formula N₃P₃F_x(CH₂SiMe₃)_6-x, where x = 2 and 4, were also prepared. The interaction of (NPF₂)₃ with Me₃SiCH₂Li involves a metal-hydrogen exchange side reaction to generate species such as N₃P₃-(CH₂SiMe₃)₅(CHSiMe₃)⁻Li⁺, hence the need for subsequent protonation. Attempts to replace the fluorine atoms in gem-N₃P₃F₄(CH₂SiMe₃)₂ by treatment with NaOCH₂CF₃ led also to C-Si bond cleavage to generate gem-N₃P₃(OCH₂CF₃)₄Me₂. No C-Si bond cleavage occurred during the attempted preparation of gem-N₃P₃(OCH₂CF₃)₂(CH₂SiMe₃)₄, and none was detected when [NP(CH₂SiMe₃)₂]₃ was treated with NaOCH₂CF₃. The structure of [NP(CH₂SiMe₃)₂]₃ has been determined by single-crystal X-ray diffraction methods. Crystals were monoclinic with a P2₁/n space group, with a = 11.012 (2) A, b = 19.851 (5) Å, c = 19.554 (8) Å, β = 90.51 (2)°, V = 4309.3 Å³, and Z = 4. A comparison is made with other alkyl- and (alkylsilyl)cyclo-triphosphazenes.

Original language	English (US)
Pages (from-to)	677-683
Number of pages	7
Journal	Organometallics
Volume	10
Issue number	3
DOIs	https://doi.org/10.1021/om00049a029
State	Published - Mar 27 1991

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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@article{90eedb3965324577a4755d0e78c02528,

title = "New Cyclic Phosphazenes with (Trimethylsilyl)methyl Side Groups: X-ray Crystal Structure of [NP(CH2SiMe3)2]3 and Its Conversion to (NPMe2)3",

abstract = "The synthesis of [NP(CH2SiMe3)2]3 has been achieved in almost quantitative yield via the reaction of Me3SiCH2Li with (NPF2)3 in tetrahydrofuran at 40 °C, followed by addition of a proton source. Treatment of [NP(CH2SiMe3)2]3 with nBu4N+F− gave (NPMe2)3 in 60% yield. Partially substituted trimers of the formula N3P3Fx(CH2SiMe3)6-x, where x = 2 and 4, were also prepared. The interaction of (NPF2)3 with Me3SiCH2Li involves a metal-hydrogen exchange side reaction to generate species such as N3P3-(CH2SiMe3)5(CHSiMe3)−Li+, hence the need for subsequent protonation. Attempts to replace the fluorine atoms in gem-N3P3F4(CH2SiMe3)2 by treatment with NaOCH2CF3 led also to C-Si bond cleavage to generate gem-N3P3(OCH2CF3)4Me2. No C-Si bond cleavage occurred during the attempted preparation of gem-N3P3(OCH2CF3)2(CH2SiMe3)4, and none was detected when [NP(CH2SiMe3)2]3 was treated with NaOCH2CF3. The structure of [NP(CH2SiMe3)2]3 has been determined by single-crystal X-ray diffraction methods. Crystals were monoclinic with a P21/n space group, with a = 11.012 (2) A, b = 19.851 (5) {\AA}, c = 19.554 (8) {\AA}, β = 90.51 (2)°, V = 4309.3 {\AA}3, and Z = 4. A comparison is made with other alkyl- and (alkylsilyl)cyclo-triphosphazenes.",

author = "Allcock, {Harry R.} and Coggio, {William D.} and Masood Parvez and Turner, {Michael L.}",

year = "1991",

month = mar,

day = "27",

doi = "10.1021/om00049a029",

language = "English (US)",

volume = "10",

pages = "677--683",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "3",

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TY - JOUR

T1 - New Cyclic Phosphazenes with (Trimethylsilyl)methyl Side Groups

T2 - X-ray Crystal Structure of [NP(CH2SiMe3)2]3 and Its Conversion to (NPMe2)3

AU - Allcock, Harry R.

AU - Coggio, William D.

AU - Parvez, Masood

AU - Turner, Michael L.

PY - 1991/3/27

Y1 - 1991/3/27

N2 - The synthesis of [NP(CH2SiMe3)2]3 has been achieved in almost quantitative yield via the reaction of Me3SiCH2Li with (NPF2)3 in tetrahydrofuran at 40 °C, followed by addition of a proton source. Treatment of [NP(CH2SiMe3)2]3 with nBu4N+F− gave (NPMe2)3 in 60% yield. Partially substituted trimers of the formula N3P3Fx(CH2SiMe3)6-x, where x = 2 and 4, were also prepared. The interaction of (NPF2)3 with Me3SiCH2Li involves a metal-hydrogen exchange side reaction to generate species such as N3P3-(CH2SiMe3)5(CHSiMe3)−Li+, hence the need for subsequent protonation. Attempts to replace the fluorine atoms in gem-N3P3F4(CH2SiMe3)2 by treatment with NaOCH2CF3 led also to C-Si bond cleavage to generate gem-N3P3(OCH2CF3)4Me2. No C-Si bond cleavage occurred during the attempted preparation of gem-N3P3(OCH2CF3)2(CH2SiMe3)4, and none was detected when [NP(CH2SiMe3)2]3 was treated with NaOCH2CF3. The structure of [NP(CH2SiMe3)2]3 has been determined by single-crystal X-ray diffraction methods. Crystals were monoclinic with a P21/n space group, with a = 11.012 (2) A, b = 19.851 (5) Å, c = 19.554 (8) Å, β = 90.51 (2)°, V = 4309.3 Å3, and Z = 4. A comparison is made with other alkyl- and (alkylsilyl)cyclo-triphosphazenes.

AB - The synthesis of [NP(CH2SiMe3)2]3 has been achieved in almost quantitative yield via the reaction of Me3SiCH2Li with (NPF2)3 in tetrahydrofuran at 40 °C, followed by addition of a proton source. Treatment of [NP(CH2SiMe3)2]3 with nBu4N+F− gave (NPMe2)3 in 60% yield. Partially substituted trimers of the formula N3P3Fx(CH2SiMe3)6-x, where x = 2 and 4, were also prepared. The interaction of (NPF2)3 with Me3SiCH2Li involves a metal-hydrogen exchange side reaction to generate species such as N3P3-(CH2SiMe3)5(CHSiMe3)−Li+, hence the need for subsequent protonation. Attempts to replace the fluorine atoms in gem-N3P3F4(CH2SiMe3)2 by treatment with NaOCH2CF3 led also to C-Si bond cleavage to generate gem-N3P3(OCH2CF3)4Me2. No C-Si bond cleavage occurred during the attempted preparation of gem-N3P3(OCH2CF3)2(CH2SiMe3)4, and none was detected when [NP(CH2SiMe3)2]3 was treated with NaOCH2CF3. The structure of [NP(CH2SiMe3)2]3 has been determined by single-crystal X-ray diffraction methods. Crystals were monoclinic with a P21/n space group, with a = 11.012 (2) A, b = 19.851 (5) Å, c = 19.554 (8) Å, β = 90.51 (2)°, V = 4309.3 Å3, and Z = 4. A comparison is made with other alkyl- and (alkylsilyl)cyclo-triphosphazenes.

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New Cyclic Phosphazenes with (Trimethylsilyl)methyl Side Groups: X-ray Crystal Structure of [NP(CH₂SiMe₃)₂]₃ and Its Conversion to (NPMe₂)₃

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