Synthesis of the 1,2,3,4-TetramethylfulveneBridged Diiron Complex (η1:η5-CH2C5Me4)Fe2(CO)6 and Its Reactions with Phosphines

Hisako Hashimoto; Hiromi Tobita; Hiroshi Ogino

doi:10.1021/om00030a030

Synthesis of the 1,2,3,4-TetramethylfulveneBridged Diiron Complex (η¹:η⁵-CH₂C₅Me₄)Fe₂(CO)₆ and Its Reactions with Phosphines

Hisako Hashimoto, Hiromi Tobita, Hiroshi Ogino

SCI - Chemistry

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

22 Citations (Scopus)

Abstract

1,2,3,4-Tetramethylfulvene was prepared by hydride abstraction from pentamethylcyclopentadienyl anion and was converted to the fulvenebridged dinuclear complex (η¹:η⁵CH₂C₅Me₄)Fe₂(CO)₆ by treatment with Fe2(CO)₉. Reaction of this complex with phosphine L (L = PMe₃, PPh₃, PH₂PCH₂PPh₂, or PPh₂H) caused replacement of a CO ligand with L to provide (η¹:η⁵-CH₂C₅Me₄)Fe₂(CO)₅L in high yield. The structure of (η¹:η⁵-CH₂C₅Me₄) Fe₂(CO)₅Ph₂ PCH₂PPh₂) was determined by X-ray crystal structure analysis: C₄₀H₃₆Fe₂O₅P₂, monoclinic, P2₁/a; a = 20.334(5) Å, b = 10.978(2) Å, c = 18.525(5) Å, β = 116.17(2)°, V = 3711.2(4) Å³, Z = 4. When Ph₂P(CH₂)₂PPh₂ was used as L, each of the phosphorus atoms made a bond to a diiron unit to give the tetranuclear complex [(η¹:η⁵-CH₂C₅Me₄)Fe₂(CO)₅]₂(μ-L). The PPh₂H complex (η¹:η⁵-CH₂C₅Me₄)Fe₂(CO)₅(PPh₂H) rearranged in hot benzene to a new phosphidobridged dinuclear complex, (C₆Me₅)Fe₂(CO)₄(η-CO)(η-PPh₂).

Original language	English
Pages (from-to)	2182-2187
Number of pages	6
Journal	Organometallics
Volume	12
Issue number	6
DOIs	https://doi.org/10.1021/om00030a030
Publication status	Published - 1993 Jan 1

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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@article{3dfc1cec5edd465186507b9ffae8fe0e,

title = "Synthesis of the 1,2,3,4-TetramethylfulveneBridged Diiron Complex (η1:η5-CH2C5Me4)Fe2(CO)6 and Its Reactions with Phosphines",

abstract = "1,2,3,4-Tetramethylfulvene was prepared by hydride abstraction from pentamethylcyclopentadienyl anion and was converted to the fulvenebridged dinuclear complex (η1:η5CH2C5Me4)Fe2(CO)6 by treatment with Fe2(CO)9. Reaction of this complex with phosphine L (L = PMe3, PPh3, PH2PCH2PPh2, or PPh2H) caused replacement of a CO ligand with L to provide (η1:η5-CH2C5Me4)Fe2(CO)5L in high yield. The structure of (η1:η5-CH2C5Me4) Fe2(CO)5Ph2 PCH2PPh2) was determined by X-ray crystal structure analysis: C40H36Fe2O5P2, monoclinic, P21/a; a = 20.334(5) {\AA}, b = 10.978(2) {\AA}, c = 18.525(5) {\AA}, β = 116.17(2)°, V = 3711.2(4) {\AA}3, Z = 4. When Ph2P(CH2)2PPh2 was used as L, each of the phosphorus atoms made a bond to a diiron unit to give the tetranuclear complex [(η1:η5-CH2C5Me4)Fe2(CO)5]2(μ-L). The PPh2H complex (η1:η5-CH2C5Me4)Fe2(CO)5(PPh2H) rearranged in hot benzene to a new phosphidobridged dinuclear complex, (C6Me5)Fe2(CO)4(η-CO)(η-PPh2).",

author = "Hisako Hashimoto and Hiromi Tobita and Hiroshi Ogino",

year = "1993",

month = jan,

day = "1",

doi = "10.1021/om00030a030",

language = "English",

volume = "12",

pages = "2182--2187",

journal = "Organometallics",

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publisher = "American Chemical Society",

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TY - JOUR

T1 - Synthesis of the 1,2,3,4-TetramethylfulveneBridged Diiron Complex (η1:η5-CH2C5Me4)Fe2(CO)6 and Its Reactions with Phosphines

AU - Hashimoto, Hisako

AU - Tobita, Hiromi

AU - Ogino, Hiroshi

PY - 1993/1/1

Y1 - 1993/1/1

N2 - 1,2,3,4-Tetramethylfulvene was prepared by hydride abstraction from pentamethylcyclopentadienyl anion and was converted to the fulvenebridged dinuclear complex (η1:η5CH2C5Me4)Fe2(CO)6 by treatment with Fe2(CO)9. Reaction of this complex with phosphine L (L = PMe3, PPh3, PH2PCH2PPh2, or PPh2H) caused replacement of a CO ligand with L to provide (η1:η5-CH2C5Me4)Fe2(CO)5L in high yield. The structure of (η1:η5-CH2C5Me4) Fe2(CO)5Ph2 PCH2PPh2) was determined by X-ray crystal structure analysis: C40H36Fe2O5P2, monoclinic, P21/a; a = 20.334(5) Å, b = 10.978(2) Å, c = 18.525(5) Å, β = 116.17(2)°, V = 3711.2(4) Å3, Z = 4. When Ph2P(CH2)2PPh2 was used as L, each of the phosphorus atoms made a bond to a diiron unit to give the tetranuclear complex [(η1:η5-CH2C5Me4)Fe2(CO)5]2(μ-L). The PPh2H complex (η1:η5-CH2C5Me4)Fe2(CO)5(PPh2H) rearranged in hot benzene to a new phosphidobridged dinuclear complex, (C6Me5)Fe2(CO)4(η-CO)(η-PPh2).

AB - 1,2,3,4-Tetramethylfulvene was prepared by hydride abstraction from pentamethylcyclopentadienyl anion and was converted to the fulvenebridged dinuclear complex (η1:η5CH2C5Me4)Fe2(CO)6 by treatment with Fe2(CO)9. Reaction of this complex with phosphine L (L = PMe3, PPh3, PH2PCH2PPh2, or PPh2H) caused replacement of a CO ligand with L to provide (η1:η5-CH2C5Me4)Fe2(CO)5L in high yield. The structure of (η1:η5-CH2C5Me4) Fe2(CO)5Ph2 PCH2PPh2) was determined by X-ray crystal structure analysis: C40H36Fe2O5P2, monoclinic, P21/a; a = 20.334(5) Å, b = 10.978(2) Å, c = 18.525(5) Å, β = 116.17(2)°, V = 3711.2(4) Å3, Z = 4. When Ph2P(CH2)2PPh2 was used as L, each of the phosphorus atoms made a bond to a diiron unit to give the tetranuclear complex [(η1:η5-CH2C5Me4)Fe2(CO)5]2(μ-L). The PPh2H complex (η1:η5-CH2C5Me4)Fe2(CO)5(PPh2H) rearranged in hot benzene to a new phosphidobridged dinuclear complex, (C6Me5)Fe2(CO)4(η-CO)(η-PPh2).

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DO - 10.1021/om00030a030

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JF - Organometallics

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Synthesis of the 1,2,3,4-TetramethylfulveneBridged Diiron Complex (η¹:η⁵-CH₂C₅Me₄)Fe₂(CO)₆ and Its Reactions with Phosphines

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