Titanium and zirconium complexes with sterically hindered aryl-substituted iminophosphoranato ligands

Musa Said; Mark Thornton-Pett; Manfred Bochmann

doi:10.1039/b105038a

Titanium and zirconium complexes with sterically hindered aryl-substituted iminophosphoranato ligands

Musa Said, Mark Thornton-Pett, Manfred Bochmann

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Abstract

The benzyliminophosphorane 4-Bu^tC₆H₄CH₂P(Ph)₂==NC₆H₂Me₃-2,4,6 reacted with TiCl₄ or ZrCl₄ to give the N-donor adducts, MCl₄{4-Bu^tC₆H₄CH₂P(Ph)₂==NC₆H₂Me₃-2,4,6}. Whereas the zirconium compound proved unreactive, solutions of the titanium analogue at 10–20 °C slowly underwent C–H activation to give the phosphoranato complex TiCl₃{4-Bu^tC₆H₄CHP(Ph)₂==NC₆H₂Me₃-2,4,6}. The trichloro complexes MCl₃{4-Bu^tC₆H₄CHP(Ph)₂==NC₆H₂Me₃-2,4,6} were also accessible from Li[4-Bu^tC₆H₄CHP(Ph)₂==NC₆H₂Me₃-2,4,6] and MCl₄ (M = Ti or Zr). The reaction of 4-Bu^tC₆H₄CH₂P(Ph)₂==NC₆H₂Me₃-2,4,6 with Zr(NMe₂)₄ in refluxing toluene led to Zr(NMe₂)₃{4-Bu^tC₆H₄CHP(Ph)₂==NC₆H₂Me₃-2,4,6}. The compound is fluxional in solution. Treatment with an excess of Me₃SiCl led to silylation of the ligand to give ZrCl₄{4-Bu^tC₆H₄CH(SiMe₃)P(Ph)₂==NC₆H₂Me₃-2,4,6}. The structures of 4-Bu^tC₆H₄CH₂P(Ph)₂==NC₆H₂Me₃-2,4,6 and Zr(NMe₂)₃{4-Bu^tC₆H₄CHP(Ph)₂==NC₆H₂Me₃-2,4,6} were determined by X-ray diffraction.

Original language	English
Pages (from-to)	2844-2849
Number of pages	6
Journal	Journal of the Chemical Society, Dalton Transactions
Issue number	19
DOIs	https://doi.org/10.1039/b105038a
Publication status	Published - 2001

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@article{0226dbcaae2549c984bf636a48a10c2e,

title = "Titanium and zirconium complexes with sterically hindered aryl-substituted iminophosphoranato ligands",

abstract = "The benzyliminophosphorane 4-ButC6H4CH2P(Ph)2==NC6H2Me3-2,4,6 reacted with TiCl4 or ZrCl4 to give the N-donor adducts, MCl4{4-ButC6H4CH2P(Ph)2==NC6H2Me3-2,4,6}. Whereas the zirconium compound proved unreactive, solutions of the titanium analogue at 10–20 °C slowly underwent C–H activation to give the phosphoranato complex TiCl3{4-ButC6H4CHP(Ph)2==NC6H2Me3-2,4,6}. The trichloro complexes MCl3{4-ButC6H4CHP(Ph)2==NC6H2Me3-2,4,6} were also accessible from Li[4-ButC6H4CHP(Ph)2==NC6H2Me3-2,4,6] and MCl4 (M = Ti or Zr). The reaction of 4-ButC6H4CH2P(Ph)2==NC6H2Me3-2,4,6 with Zr(NMe2)4 in refluxing toluene led to Zr(NMe2)3{4-ButC6H4CHP(Ph)2==NC6H2Me3-2,4,6}. The compound is fluxional in solution. Treatment with an excess of Me3SiCl led to silylation of the ligand to give ZrCl4{4-ButC6H4CH(SiMe3)P(Ph)2==NC6H2Me3-2,4,6}. The structures of 4-ButC6H4CH2P(Ph)2==NC6H2Me3-2,4,6 and Zr(NMe2)3{4-ButC6H4CHP(Ph)2==NC6H2Me3-2,4,6} were determined by X-ray diffraction.",

author = "Musa Said and Mark Thornton-Pett and Manfred Bochmann",

year = "2001",

doi = "10.1039/b105038a",

language = "English",

pages = "2844--2849",

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

issn = "1477-9234",

publisher = "Royal Society of Chemistry",

number = "19",

}

TY - JOUR

T1 - Titanium and zirconium complexes with sterically hindered aryl-substituted iminophosphoranato ligands

AU - Said, Musa

AU - Thornton-Pett, Mark

AU - Bochmann, Manfred

PY - 2001

Y1 - 2001

N2 - The benzyliminophosphorane 4-ButC6H4CH2P(Ph)2==NC6H2Me3-2,4,6 reacted with TiCl4 or ZrCl4 to give the N-donor adducts, MCl4{4-ButC6H4CH2P(Ph)2==NC6H2Me3-2,4,6}. Whereas the zirconium compound proved unreactive, solutions of the titanium analogue at 10–20 °C slowly underwent C–H activation to give the phosphoranato complex TiCl3{4-ButC6H4CHP(Ph)2==NC6H2Me3-2,4,6}. The trichloro complexes MCl3{4-ButC6H4CHP(Ph)2==NC6H2Me3-2,4,6} were also accessible from Li[4-ButC6H4CHP(Ph)2==NC6H2Me3-2,4,6] and MCl4 (M = Ti or Zr). The reaction of 4-ButC6H4CH2P(Ph)2==NC6H2Me3-2,4,6 with Zr(NMe2)4 in refluxing toluene led to Zr(NMe2)3{4-ButC6H4CHP(Ph)2==NC6H2Me3-2,4,6}. The compound is fluxional in solution. Treatment with an excess of Me3SiCl led to silylation of the ligand to give ZrCl4{4-ButC6H4CH(SiMe3)P(Ph)2==NC6H2Me3-2,4,6}. The structures of 4-ButC6H4CH2P(Ph)2==NC6H2Me3-2,4,6 and Zr(NMe2)3{4-ButC6H4CHP(Ph)2==NC6H2Me3-2,4,6} were determined by X-ray diffraction.

AB - The benzyliminophosphorane 4-ButC6H4CH2P(Ph)2==NC6H2Me3-2,4,6 reacted with TiCl4 or ZrCl4 to give the N-donor adducts, MCl4{4-ButC6H4CH2P(Ph)2==NC6H2Me3-2,4,6}. Whereas the zirconium compound proved unreactive, solutions of the titanium analogue at 10–20 °C slowly underwent C–H activation to give the phosphoranato complex TiCl3{4-ButC6H4CHP(Ph)2==NC6H2Me3-2,4,6}. The trichloro complexes MCl3{4-ButC6H4CHP(Ph)2==NC6H2Me3-2,4,6} were also accessible from Li[4-ButC6H4CHP(Ph)2==NC6H2Me3-2,4,6] and MCl4 (M = Ti or Zr). The reaction of 4-ButC6H4CH2P(Ph)2==NC6H2Me3-2,4,6 with Zr(NMe2)4 in refluxing toluene led to Zr(NMe2)3{4-ButC6H4CHP(Ph)2==NC6H2Me3-2,4,6}. The compound is fluxional in solution. Treatment with an excess of Me3SiCl led to silylation of the ligand to give ZrCl4{4-ButC6H4CH(SiMe3)P(Ph)2==NC6H2Me3-2,4,6}. The structures of 4-ButC6H4CH2P(Ph)2==NC6H2Me3-2,4,6 and Zr(NMe2)3{4-ButC6H4CHP(Ph)2==NC6H2Me3-2,4,6} were determined by X-ray diffraction.

U2 - 10.1039/b105038a

DO - 10.1039/b105038a

M3 - Article

SN - 1477-9234

SP - 2844

EP - 2849

JO - Journal of the Chemical Society, Dalton Transactions

JF - Journal of the Chemical Society, Dalton Transactions

IS - 19

ER -