Synthesis of Strained Ferrocenylorganocyclophosphazenes: X-ray Crystal Structures of N3P3(OCH2CF3)4(η-C5H4)2Fe, N3P3(OPh)4(η-C5H4)2Fe, and N3P3Ph2(OCH2CF3)2(η-C5H4)2Fe

Harry R. Allcock; Jeffrey A. Dodge; Ian Manners; Masood Parvez; Geoffrey H. Riding; Karyn B. Visscher

doi:10.1021/om00055a023

Synthesis of Strained Ferrocenylorganocyclophosphazenes: X-ray Crystal Structures of N₃P₃(OCH₂CF₃)₄(η-C₅H₄)₂Fe, N₃P₃(OPh)₄(η-C₅H₄)₂Fe, and N₃P₃Ph₂(OCH₂CF₃)₂(η-C₅H₄)₂Fe

Harry R. Allcock, Jeffrey A. Dodge, Ian Manners, Masood Parvez, Geoffrey H. Riding, Karyn B. Visscher

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

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Abstract

A series of transannular ferrocenylcyclotriphosphazenes were synthesized for studies of the relationship between molecular structure and polymerization behavior. Species N₃P₃(OCH₂CF₃)₄(η-C₆H₄)₂Fe and N₃P₃(OPh)₄(η-C₆H₄)₂Fe were synthesized by the reaction of N₃P₃F₄(η-C₅H₄)₂Fe with NaOCH₂CF₃ and NaOPh, respectively. Cyclic trimers N₃P₃R(OCH₂CF₃)₃(η-C₅H₄)₂Fe [R = OPh, R = Me, R = Ph (gem to Cp) and R = Ph (non-gem to Cp)] were prepared by reactions of the appropriate fluoroferrocenylphosphazene precursors [N₃P₃(OPh)F₃(η -C₅H₄)₂Fe, N₃P₃MeF₃(η-C₅H₄)₂Fe, N₃P₃PhF₃(η-C₅H₄)₂Fe, and N₃P₃PhF₃(η-C₆H₄)₂Fe] with NaOCH₂CF₃. The synthesis of N₃P₃Ph₂(OCH₂CF₃)₂(η-C₅H₄)₂Fe, (Ph groups non-gem to Cp) was achieved via the reaction of gem-N₃P₃F₄Ph₂ with dilithioferrocene to give N₃P₃Ph₂F₂(η-C₅H₄)₂Fe, followed by treatment with NaOCH₂CF₃. Treatment of N₃P₃Ph₂F₂(η-C₅H₄)₂Fe with NaOCH₂CF₃ yielded N₃P₃Ph₂(OCH₂CF₃)₂(η-C₅H₄)₂Fe (Ph groups gem to Cp). A 1-equiv amount of NaOPh reacts with N₃P₃F₄(η-C₅H₄)₂Fe to form a mixture of cis- and trans-N₃P₃(OPh)F₃(η-C₅H₄)₂Fe. The molecular structures of N₃P₃(OCH₂CF₃)₄(η-C₅H₄)₂Fe, N₃P₃(OPh)₄(η-C₅H₄)₂Fe, and N₃P₃Ph₂(OCH₂CF₃)₂(η-C₅H₄)₂Fe were de termined by single-crystal X-ray diffraction. All were found to possess nonplanar, strained cyclotriphosphazene rings. Crystals of N₃P₃(OCH₂CF₃)₄(η-C₅H₄)₂Fe are monoclinic with space group P2₁/C, with α = 9.529 (5) Å, b = 14.515 (2) Å, c = 19.012 Å, β = 97.94 (2)°, V = 2605.8 Å³, and Z = 4. Crystals of N₃P₃(OPh)₄(η-C₅H₄)₂Fe are orthorhombic of space group P2₁2₁2₁ with a = 9.890 (2) Å, b = 15.962 (3) Å, c = 19.629(3) Å, V = 3098.8 Å³, and Z = 4. The diphenyl species, N₃P₃Ph₂(OCH₂CF₃)₂(η-C₅H₄)₂Fe, crystallizes in the trigonal space group R3 (hexagonal axes) with α = 23.954 (8)Å, b = 23.94 (1) Å, c = 13.17 (1) Å, V = 6544 Å³, and Z = 9.

Original language	English (US)
Pages (from-to)	3098-3104
Number of pages	7
Journal	Organometallics
Volume	10
Issue number	9
DOIs	https://doi.org/10.1021/om00055a023
State	Published - Sep 1 1991

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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10.1021/om00055a023

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@article{078898d6a77a413ba7b7f528e613059a,

title = "Synthesis of Strained Ferrocenylorganocyclophosphazenes: X-ray Crystal Structures of N3P3(OCH2CF3)4(η-C5H4)2Fe, N3P3(OPh)4(η-C5H4)2Fe, and N3P3Ph2(OCH2CF3)2(η-C5H4)2Fe",

abstract = "A series of transannular ferrocenylcyclotriphosphazenes were synthesized for studies of the relationship between molecular structure and polymerization behavior. Species N3P3(OCH2CF3)4(η-C6H4)2Fe and N3P3(OPh)4(η-C6H4)2Fe were synthesized by the reaction of N3P3F4(η-C5H4)2Fe with NaOCH2CF3 and NaOPh, respectively. Cyclic trimers N3P3R(OCH2CF3)3(η-C5H4)2Fe [R = OPh, R = Me, R = Ph (gem to Cp) and R = Ph (non-gem to Cp)] were prepared by reactions of the appropriate fluoroferrocenylphosphazene precursors [N3P3(OPh)F3(η -C5H4)2Fe, N3P3MeF3(η-C5H4)2Fe, N3P3PhF3(η-C5H4)2Fe, and N3P3PhF3(η-C6H4)2Fe] with NaOCH2CF3. The synthesis of N3P3Ph2(OCH2CF3)2(η-C5H4)2Fe, (Ph groups non-gem to Cp) was achieved via the reaction of gem-N3P3F4Ph2 with dilithioferrocene to give N3P3Ph2F2(η-C5H4)2Fe, followed by treatment with NaOCH2CF3. Treatment of N3P3Ph2F2(η-C5H4)2Fe with NaOCH2CF3 yielded N3P3Ph2(OCH2CF3)2(η-C5H4)2Fe (Ph groups gem to Cp). A 1-equiv amount of NaOPh reacts with N3P3F4(η-C5H4)2Fe to form a mixture of cis- and trans-N3P3(OPh)F3(η-C5H4)2Fe. The molecular structures of N3P3(OCH2CF3)4(η-C5H4)2Fe, N3P3(OPh)4(η-C5H4)2Fe, and N3P3Ph2(OCH2CF3)2(η-C5H4)2Fe were de termined by single-crystal X-ray diffraction. All were found to possess nonplanar, strained cyclotriphosphazene rings. Crystals of N3P3(OCH2CF3)4(η-C5H4)2Fe are monoclinic with space group P21/C, with α = 9.529 (5) {\AA}, b = 14.515 (2) {\AA}, c = 19.012 {\AA}, β = 97.94 (2)°, V = 2605.8 {\AA}3, and Z = 4. Crystals of N3P3(OPh)4(η-C5H4)2Fe are orthorhombic of space group P212121 with a = 9.890 (2) {\AA}, b = 15.962 (3) {\AA}, c = 19.629(3) {\AA}, V = 3098.8 {\AA}3, and Z = 4. The diphenyl species, N3P3Ph2(OCH2CF3)2(η-C5H4)2Fe, crystallizes in the trigonal space group R3 (hexagonal axes) with α = 23.954 (8){\AA}, b = 23.94 (1) {\AA}, c = 13.17 (1) {\AA}, V = 6544 {\AA}3, and Z = 9.",

author = "Allcock, {Harry R.} and Dodge, {Jeffrey A.} and Ian Manners and Masood Parvez and Riding, {Geoffrey H.} and Visscher, {Karyn B.}",

year = "1991",

month = sep,

day = "1",

doi = "10.1021/om00055a023",

language = "English (US)",

volume = "10",

pages = "3098--3104",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "9",

}

TY - JOUR

T1 - Synthesis of Strained Ferrocenylorganocyclophosphazenes

T2 - X-ray Crystal Structures of N3P3(OCH2CF3)4(η-C5H4)2Fe, N3P3(OPh)4(η-C5H4)2Fe, and N3P3Ph2(OCH2CF3)2(η-C5H4)2Fe

AU - Allcock, Harry R.

AU - Dodge, Jeffrey A.

AU - Manners, Ian

AU - Parvez, Masood

AU - Riding, Geoffrey H.

AU - Visscher, Karyn B.

PY - 1991/9/1

Y1 - 1991/9/1

N2 - A series of transannular ferrocenylcyclotriphosphazenes were synthesized for studies of the relationship between molecular structure and polymerization behavior. Species N3P3(OCH2CF3)4(η-C6H4)2Fe and N3P3(OPh)4(η-C6H4)2Fe were synthesized by the reaction of N3P3F4(η-C5H4)2Fe with NaOCH2CF3 and NaOPh, respectively. Cyclic trimers N3P3R(OCH2CF3)3(η-C5H4)2Fe [R = OPh, R = Me, R = Ph (gem to Cp) and R = Ph (non-gem to Cp)] were prepared by reactions of the appropriate fluoroferrocenylphosphazene precursors [N3P3(OPh)F3(η -C5H4)2Fe, N3P3MeF3(η-C5H4)2Fe, N3P3PhF3(η-C5H4)2Fe, and N3P3PhF3(η-C6H4)2Fe] with NaOCH2CF3. The synthesis of N3P3Ph2(OCH2CF3)2(η-C5H4)2Fe, (Ph groups non-gem to Cp) was achieved via the reaction of gem-N3P3F4Ph2 with dilithioferrocene to give N3P3Ph2F2(η-C5H4)2Fe, followed by treatment with NaOCH2CF3. Treatment of N3P3Ph2F2(η-C5H4)2Fe with NaOCH2CF3 yielded N3P3Ph2(OCH2CF3)2(η-C5H4)2Fe (Ph groups gem to Cp). A 1-equiv amount of NaOPh reacts with N3P3F4(η-C5H4)2Fe to form a mixture of cis- and trans-N3P3(OPh)F3(η-C5H4)2Fe. The molecular structures of N3P3(OCH2CF3)4(η-C5H4)2Fe, N3P3(OPh)4(η-C5H4)2Fe, and N3P3Ph2(OCH2CF3)2(η-C5H4)2Fe were de termined by single-crystal X-ray diffraction. All were found to possess nonplanar, strained cyclotriphosphazene rings. Crystals of N3P3(OCH2CF3)4(η-C5H4)2Fe are monoclinic with space group P21/C, with α = 9.529 (5) Å, b = 14.515 (2) Å, c = 19.012 Å, β = 97.94 (2)°, V = 2605.8 Å3, and Z = 4. Crystals of N3P3(OPh)4(η-C5H4)2Fe are orthorhombic of space group P212121 with a = 9.890 (2) Å, b = 15.962 (3) Å, c = 19.629(3) Å, V = 3098.8 Å3, and Z = 4. The diphenyl species, N3P3Ph2(OCH2CF3)2(η-C5H4)2Fe, crystallizes in the trigonal space group R3 (hexagonal axes) with α = 23.954 (8)Å, b = 23.94 (1) Å, c = 13.17 (1) Å, V = 6544 Å3, and Z = 9.

AB - A series of transannular ferrocenylcyclotriphosphazenes were synthesized for studies of the relationship between molecular structure and polymerization behavior. Species N3P3(OCH2CF3)4(η-C6H4)2Fe and N3P3(OPh)4(η-C6H4)2Fe were synthesized by the reaction of N3P3F4(η-C5H4)2Fe with NaOCH2CF3 and NaOPh, respectively. Cyclic trimers N3P3R(OCH2CF3)3(η-C5H4)2Fe [R = OPh, R = Me, R = Ph (gem to Cp) and R = Ph (non-gem to Cp)] were prepared by reactions of the appropriate fluoroferrocenylphosphazene precursors [N3P3(OPh)F3(η -C5H4)2Fe, N3P3MeF3(η-C5H4)2Fe, N3P3PhF3(η-C5H4)2Fe, and N3P3PhF3(η-C6H4)2Fe] with NaOCH2CF3. The synthesis of N3P3Ph2(OCH2CF3)2(η-C5H4)2Fe, (Ph groups non-gem to Cp) was achieved via the reaction of gem-N3P3F4Ph2 with dilithioferrocene to give N3P3Ph2F2(η-C5H4)2Fe, followed by treatment with NaOCH2CF3. Treatment of N3P3Ph2F2(η-C5H4)2Fe with NaOCH2CF3 yielded N3P3Ph2(OCH2CF3)2(η-C5H4)2Fe (Ph groups gem to Cp). A 1-equiv amount of NaOPh reacts with N3P3F4(η-C5H4)2Fe to form a mixture of cis- and trans-N3P3(OPh)F3(η-C5H4)2Fe. The molecular structures of N3P3(OCH2CF3)4(η-C5H4)2Fe, N3P3(OPh)4(η-C5H4)2Fe, and N3P3Ph2(OCH2CF3)2(η-C5H4)2Fe were de termined by single-crystal X-ray diffraction. All were found to possess nonplanar, strained cyclotriphosphazene rings. Crystals of N3P3(OCH2CF3)4(η-C5H4)2Fe are monoclinic with space group P21/C, with α = 9.529 (5) Å, b = 14.515 (2) Å, c = 19.012 Å, β = 97.94 (2)°, V = 2605.8 Å3, and Z = 4. Crystals of N3P3(OPh)4(η-C5H4)2Fe are orthorhombic of space group P212121 with a = 9.890 (2) Å, b = 15.962 (3) Å, c = 19.629(3) Å, V = 3098.8 Å3, and Z = 4. The diphenyl species, N3P3Ph2(OCH2CF3)2(η-C5H4)2Fe, crystallizes in the trigonal space group R3 (hexagonal axes) with α = 23.954 (8)Å, b = 23.94 (1) Å, c = 13.17 (1) Å, V = 6544 Å3, and Z = 9.

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U2 - 10.1021/om00055a023

DO - 10.1021/om00055a023

M3 - Article

AN - SCOPUS:0000165974

SN - 0276-7333

VL - 10

SP - 3098

EP - 3104

JO - Organometallics

JF - Organometallics

IS - 9

ER -

Synthesis of Strained Ferrocenylorganocyclophosphazenes: X-ray Crystal Structures of N₃P₃(OCH₂CF₃)₄(η-C₅H₄)₂Fe, N₃P₃(OPh)₄(η-C₅H₄)₂Fe, and N₃P₃Ph₂(OCH₂CF₃)₂(η-C₅H₄)₂Fe

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