Cyclic and short-chain linear phosphazenes with hindered aryloxy side groups

Harry R. Allcock; Dennis C. Ngo; Masood Parvez; Karyn Visscher

doi:10.1039/DT9920001687

Cyclic and short-chain linear phosphazenes with hindered aryloxy side groups

Harry R. Allcock
, Dennis C. Ngo
, Masood Parvez
, Karyn Visscher

Research output: Contribution to journal › Article › peer-review

36 Scopus citations

Abstract

A series of short-chain and cyclic phosphazenes bearing o-dichloro- and o-dimethyl-phenoxy groups have been synthesised, and their structures studied by X-ray crystallography. These compounds are small-molecule models for the corresponding linear high polymers. Structural parameters: N₃P₃Cl₅(OC₆H₃Cl ₂-o) 1, a = 8.081(4), b = 8.074(2), c = 25.868(3) Å, β = 91.11(2)°, space group P2₁/c, Z = 4; gem-N₃P₃Cl₄(OC₆H₃Cl ₂-o)₂ 2, a = 18.856(5), b = 8.002(2), c = 16.124(2) Å, β = 114.89(2)°, space group P2₁/c, Z = 4; N₃P₃Cl₂(OC₆H₃Cl ₂-o)₄ 4, a = 7.975(3), b = 18.373(4), c = 22.225(3) Å, β = 90.35(2)°, space group P2₁/n, Z = 4; [NP(OC₆H₃Cl₂-o)₂]₃ 5, a = 12.021(4), b = 19.938(5), c = 18.379(11) Å, β = 90.84(5)°, space group P2₁/n, Z = 4; gem-N₄P₄Cl₄(OC₆H₃Cl ₂-o)₄ 6, a = 10.806(2), b = 10.861(2), c = 17.075(7) Å, α = 89.33(4), β = 80.79(3), γ = 68.44(2)°, space group P1, Z = 2; gem-N₃P₃Cl₄(OC₆H₃Me ₂-o)₂ 7, a = 9.470(3), b = 18.481(12), c = 13.087(8) Å, β = 94.56(4)°, space group P2₁/n, Z = 4; [NP(OC₆H₃Me₂-o)₂]₃ 8, a = 20.560(5), b = 20.580(9), c = 22.085(4) Å, α = β = γ = 90.0°, space group P4/ncc, Z = 8; OPCl₂NP(OC₆H₃Cl₂-o)₃ 9, a = 14.319(4), b = 16.837(4), c = 20.660(8) Å, space group Pbca, Z = 8; OPCl(OC₆H₃Me₂-o)NPCl(OC₆H ₃Me₂-o)NP(OC₆H₃Me ₂-o)₃ 10, a = 15.212(3), b = 18.965(1), c = 14.559(2) Å, β = 102.96(2)°, space group P2₁/c, Z = 4. Despite the bulkiness of the o-dichloro- and o-dimethyl-phenoxy groups, their introduction into the phosphazene structure followed a geminal substitution pathway during the early stages of the reaction. In the reactions with the linear short-chain oligomers these nucleophiles preferentially attacked at the terminal PCl₃ rather than at the PCl units in the middle of the chain or those associated with the phosphoryl group. The structure of compound 10 revealed a distorted trans-trans conformation for the PN skeleton, in contrast to the cis-trans arrangement generally believed to exist for linear phosphazene high polymers.

Original language	English (US)
Pages (from-to)	1687-1699
Number of pages	13
Journal	Journal of the Chemical Society, Dalton Transactions
Issue number	10
DOIs	https://doi.org/10.1039/DT9920001687
State	Published - 1992

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General Chemistry

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10.1039/DT9920001687

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@article{4c6e8c8e33244d55a2f4d09d482a5ba4,

title = "Cyclic and short-chain linear phosphazenes with hindered aryloxy side groups",

abstract = "A series of short-chain and cyclic phosphazenes bearing o-dichloro- and o-dimethyl-phenoxy groups have been synthesised, and their structures studied by X-ray crystallography. These compounds are small-molecule models for the corresponding linear high polymers. Structural parameters: N3P3Cl5(OC6H3Cl 2-o) 1, a = 8.081(4), b = 8.074(2), c = 25.868(3) {\AA}, β = 91.11(2)°, space group P21/c, Z = 4; gem-N3P3Cl4(OC6H3Cl 2-o)2 2, a = 18.856(5), b = 8.002(2), c = 16.124(2) {\AA}, β = 114.89(2)°, space group P21/c, Z = 4; N3P3Cl2(OC6H3Cl 2-o)4 4, a = 7.975(3), b = 18.373(4), c = 22.225(3) {\AA}, β = 90.35(2)°, space group P21/n, Z = 4; [NP(OC6H3Cl2-o)2]3 5, a = 12.021(4), b = 19.938(5), c = 18.379(11) {\AA}, β = 90.84(5)°, space group P21/n, Z = 4; gem-N4P4Cl4(OC6H3Cl 2-o)4 6, a = 10.806(2), b = 10.861(2), c = 17.075(7) {\AA}, α = 89.33(4), β = 80.79(3), γ = 68.44(2)°, space group P1, Z = 2; gem-N3P3Cl4(OC6H3Me 2-o)2 7, a = 9.470(3), b = 18.481(12), c = 13.087(8) {\AA}, β = 94.56(4)°, space group P21/n, Z = 4; [NP(OC6H3Me2-o)2]3 8, a = 20.560(5), b = 20.580(9), c = 22.085(4) {\AA}, α = β = γ = 90.0°, space group P4/ncc, Z = 8; OPCl2NP(OC6H3Cl2-o)3 9, a = 14.319(4), b = 16.837(4), c = 20.660(8) {\AA}, space group Pbca, Z = 8; OPCl(OC6H3Me2-o)NPCl(OC6H 3Me2-o)NP(OC6H3Me 2-o)3 10, a = 15.212(3), b = 18.965(1), c = 14.559(2) {\AA}, β = 102.96(2)°, space group P21/c, Z = 4. Despite the bulkiness of the o-dichloro- and o-dimethyl-phenoxy groups, their introduction into the phosphazene structure followed a geminal substitution pathway during the early stages of the reaction. In the reactions with the linear short-chain oligomers these nucleophiles preferentially attacked at the terminal PCl3 rather than at the PCl units in the middle of the chain or those associated with the phosphoryl group. The structure of compound 10 revealed a distorted trans-trans conformation for the PN skeleton, in contrast to the cis-trans arrangement generally believed to exist for linear phosphazene high polymers.",

author = "Allcock, \{Harry R.\} and Ngo, \{Dennis C.\} and Masood Parvez and Karyn Visscher",

year = "1992",

doi = "10.1039/DT9920001687",

language = "English (US)",

pages = "1687--1699",

journal = "Journal of the Chemical Society, Dalton Transactions",

issn = "1472-7773",

number = "10",

}

TY - JOUR

T1 - Cyclic and short-chain linear phosphazenes with hindered aryloxy side groups

AU - Allcock, Harry R.

AU - Ngo, Dennis C.

AU - Parvez, Masood

AU - Visscher, Karyn

PY - 1992

Y1 - 1992

N2 - A series of short-chain and cyclic phosphazenes bearing o-dichloro- and o-dimethyl-phenoxy groups have been synthesised, and their structures studied by X-ray crystallography. These compounds are small-molecule models for the corresponding linear high polymers. Structural parameters: N3P3Cl5(OC6H3Cl 2-o) 1, a = 8.081(4), b = 8.074(2), c = 25.868(3) Å, β = 91.11(2)°, space group P21/c, Z = 4; gem-N3P3Cl4(OC6H3Cl 2-o)2 2, a = 18.856(5), b = 8.002(2), c = 16.124(2) Å, β = 114.89(2)°, space group P21/c, Z = 4; N3P3Cl2(OC6H3Cl 2-o)4 4, a = 7.975(3), b = 18.373(4), c = 22.225(3) Å, β = 90.35(2)°, space group P21/n, Z = 4; [NP(OC6H3Cl2-o)2]3 5, a = 12.021(4), b = 19.938(5), c = 18.379(11) Å, β = 90.84(5)°, space group P21/n, Z = 4; gem-N4P4Cl4(OC6H3Cl 2-o)4 6, a = 10.806(2), b = 10.861(2), c = 17.075(7) Å, α = 89.33(4), β = 80.79(3), γ = 68.44(2)°, space group P1, Z = 2; gem-N3P3Cl4(OC6H3Me 2-o)2 7, a = 9.470(3), b = 18.481(12), c = 13.087(8) Å, β = 94.56(4)°, space group P21/n, Z = 4; [NP(OC6H3Me2-o)2]3 8, a = 20.560(5), b = 20.580(9), c = 22.085(4) Å, α = β = γ = 90.0°, space group P4/ncc, Z = 8; OPCl2NP(OC6H3Cl2-o)3 9, a = 14.319(4), b = 16.837(4), c = 20.660(8) Å, space group Pbca, Z = 8; OPCl(OC6H3Me2-o)NPCl(OC6H 3Me2-o)NP(OC6H3Me 2-o)3 10, a = 15.212(3), b = 18.965(1), c = 14.559(2) Å, β = 102.96(2)°, space group P21/c, Z = 4. Despite the bulkiness of the o-dichloro- and o-dimethyl-phenoxy groups, their introduction into the phosphazene structure followed a geminal substitution pathway during the early stages of the reaction. In the reactions with the linear short-chain oligomers these nucleophiles preferentially attacked at the terminal PCl3 rather than at the PCl units in the middle of the chain or those associated with the phosphoryl group. The structure of compound 10 revealed a distorted trans-trans conformation for the PN skeleton, in contrast to the cis-trans arrangement generally believed to exist for linear phosphazene high polymers.

AB - A series of short-chain and cyclic phosphazenes bearing o-dichloro- and o-dimethyl-phenoxy groups have been synthesised, and their structures studied by X-ray crystallography. These compounds are small-molecule models for the corresponding linear high polymers. Structural parameters: N3P3Cl5(OC6H3Cl 2-o) 1, a = 8.081(4), b = 8.074(2), c = 25.868(3) Å, β = 91.11(2)°, space group P21/c, Z = 4; gem-N3P3Cl4(OC6H3Cl 2-o)2 2, a = 18.856(5), b = 8.002(2), c = 16.124(2) Å, β = 114.89(2)°, space group P21/c, Z = 4; N3P3Cl2(OC6H3Cl 2-o)4 4, a = 7.975(3), b = 18.373(4), c = 22.225(3) Å, β = 90.35(2)°, space group P21/n, Z = 4; [NP(OC6H3Cl2-o)2]3 5, a = 12.021(4), b = 19.938(5), c = 18.379(11) Å, β = 90.84(5)°, space group P21/n, Z = 4; gem-N4P4Cl4(OC6H3Cl 2-o)4 6, a = 10.806(2), b = 10.861(2), c = 17.075(7) Å, α = 89.33(4), β = 80.79(3), γ = 68.44(2)°, space group P1, Z = 2; gem-N3P3Cl4(OC6H3Me 2-o)2 7, a = 9.470(3), b = 18.481(12), c = 13.087(8) Å, β = 94.56(4)°, space group P21/n, Z = 4; [NP(OC6H3Me2-o)2]3 8, a = 20.560(5), b = 20.580(9), c = 22.085(4) Å, α = β = γ = 90.0°, space group P4/ncc, Z = 8; OPCl2NP(OC6H3Cl2-o)3 9, a = 14.319(4), b = 16.837(4), c = 20.660(8) Å, space group Pbca, Z = 8; OPCl(OC6H3Me2-o)NPCl(OC6H 3Me2-o)NP(OC6H3Me 2-o)3 10, a = 15.212(3), b = 18.965(1), c = 14.559(2) Å, β = 102.96(2)°, space group P21/c, Z = 4. Despite the bulkiness of the o-dichloro- and o-dimethyl-phenoxy groups, their introduction into the phosphazene structure followed a geminal substitution pathway during the early stages of the reaction. In the reactions with the linear short-chain oligomers these nucleophiles preferentially attacked at the terminal PCl3 rather than at the PCl units in the middle of the chain or those associated with the phosphoryl group. The structure of compound 10 revealed a distorted trans-trans conformation for the PN skeleton, in contrast to the cis-trans arrangement generally believed to exist for linear phosphazene high polymers.

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UR - https://www.scopus.com/pages/publications/37049076832#tab=citedBy

U2 - 10.1039/DT9920001687

DO - 10.1039/DT9920001687

M3 - Article

AN - SCOPUS:37049076832

SN - 1472-7773

SP - 1687

EP - 1699

JO - Journal of the Chemical Society, Dalton Transactions

JF - Journal of the Chemical Society, Dalton Transactions

IS - 10

ER -

Cyclic and short-chain linear phosphazenes with hindered aryloxy side groups

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