The reactivity of trimethylsilyliminophosphines towards titanium and zirconium halides

Mark J. Sarsfield; Musa Said; Mark Thornton-Pett; Lee A. Gerrard; Manfred Bochmann

doi:10.1039/b009082o

The reactivity of trimethylsilyliminophosphines towards titanium and zirconium halides

Mark J. Sarsfield, Musa Said, Mark Thornton-Pett, Lee A. Gerrard, Manfred Bochmann

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Abstract

Zirconium tetrachloride reacted with C₂H₄(Ph₂P=NSiMe₃)₂-1,2 1 under C–H activation to give the NCN chelate complex ZrCl₃{?³-N,C,N'-C₂H₃(Ph₂P=NSiMe₃)₂}, while the reaction with C₅H₃N(Ph₂P=NSiMe₃)₂-2,6 gave an N-donor adduct. Cp*TiCl₃ reacts with trimethylsilyliminophosphines under dehalosilylation in all cases. In contrast to 1, the potentially C–N chelating benzylphosphinimine (4-Bu^tC₆H₄CH₂)Ph₂P=NSiMe₃ undergoes dehalosilylation with TiCl₄ in preference to C–H activation, while prolonged reflux with ZrCl₄ affords the salt [4-Bu^tC₆H₄CH₂P(Ph)₂NHSiMe₃]₂[Zr₂Cl₁₀]. The molecular structures of the latter, ZrCl₃{C₂H₃(Ph₂PNSiMe₃)₂}, C₅H₃N(Ph₂P=NTiCl₂Cp*)₂-2,6, and TiCl₂Cp*{N=PPh₂CH₂C₆H₄Bu^t-4} have been determined by X-ray diffraction.

Original language	English
Pages (from-to)	822-827
Number of pages	6
Journal	Journal of the Chemical Society, Dalton Transactions
Issue number	6
DOIs	https://doi.org/10.1039/b009082o
Publication status	Published - 22 Feb 2001

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@article{5f44687462864506a20710ae3a73fdca,

title = "The reactivity of trimethylsilyliminophosphines towards titanium and zirconium halides",

abstract = "Zirconium tetrachloride reacted with C2H4(Ph2P=NSiMe3)2-1,2 1 under C–H activation to give the NCN chelate complex ZrCl3{?3-N,C,N'-C2H3(Ph2P=NSiMe3)2}, while the reaction with C5H3N(Ph2P=NSiMe3)2-2,6 gave an N-donor adduct. Cp*TiCl3 reacts with trimethylsilyliminophosphines under dehalosilylation in all cases. In contrast to 1, the potentially C–N chelating benzylphosphinimine (4-ButC6H4CH2)Ph2P=NSiMe3 undergoes dehalosilylation with TiCl4 in preference to C–H activation, while prolonged reflux with ZrCl4 affords the salt [4-ButC6H4CH2P(Ph)2NHSiMe3]2[Zr2Cl10]. The molecular structures of the latter, ZrCl3{C2H3(Ph2PNSiMe3)2}, C5H3N(Ph2P=NTiCl2Cp*)2-2,6, and TiCl2Cp*{N=PPh2CH2C6H4But-4} have been determined by X-ray diffraction.",

author = "Sarsfield, {Mark J.} and Musa Said and Mark Thornton-Pett and Gerrard, {Lee A.} and Manfred Bochmann",

year = "2001",

month = feb,

day = "22",

doi = "10.1039/b009082o",

language = "English",

pages = "822--827",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "6",

}

TY - JOUR

T1 - The reactivity of trimethylsilyliminophosphines towards titanium and zirconium halides

AU - Sarsfield, Mark J.

AU - Said, Musa

AU - Thornton-Pett, Mark

AU - Gerrard, Lee A.

AU - Bochmann, Manfred

PY - 2001/2/22

Y1 - 2001/2/22

N2 - Zirconium tetrachloride reacted with C2H4(Ph2P=NSiMe3)2-1,2 1 under C–H activation to give the NCN chelate complex ZrCl3{?3-N,C,N'-C2H3(Ph2P=NSiMe3)2}, while the reaction with C5H3N(Ph2P=NSiMe3)2-2,6 gave an N-donor adduct. Cp*TiCl3 reacts with trimethylsilyliminophosphines under dehalosilylation in all cases. In contrast to 1, the potentially C–N chelating benzylphosphinimine (4-ButC6H4CH2)Ph2P=NSiMe3 undergoes dehalosilylation with TiCl4 in preference to C–H activation, while prolonged reflux with ZrCl4 affords the salt [4-ButC6H4CH2P(Ph)2NHSiMe3]2[Zr2Cl10]. The molecular structures of the latter, ZrCl3{C2H3(Ph2PNSiMe3)2}, C5H3N(Ph2P=NTiCl2Cp*)2-2,6, and TiCl2Cp*{N=PPh2CH2C6H4But-4} have been determined by X-ray diffraction.

AB - Zirconium tetrachloride reacted with C2H4(Ph2P=NSiMe3)2-1,2 1 under C–H activation to give the NCN chelate complex ZrCl3{?3-N,C,N'-C2H3(Ph2P=NSiMe3)2}, while the reaction with C5H3N(Ph2P=NSiMe3)2-2,6 gave an N-donor adduct. Cp*TiCl3 reacts with trimethylsilyliminophosphines under dehalosilylation in all cases. In contrast to 1, the potentially C–N chelating benzylphosphinimine (4-ButC6H4CH2)Ph2P=NSiMe3 undergoes dehalosilylation with TiCl4 in preference to C–H activation, while prolonged reflux with ZrCl4 affords the salt [4-ButC6H4CH2P(Ph)2NHSiMe3]2[Zr2Cl10]. The molecular structures of the latter, ZrCl3{C2H3(Ph2PNSiMe3)2}, C5H3N(Ph2P=NTiCl2Cp*)2-2,6, and TiCl2Cp*{N=PPh2CH2C6H4But-4} have been determined by X-ray diffraction.

U2 - 10.1039/b009082o

DO - 10.1039/b009082o

M3 - Article

SP - 822

EP - 827

JO - Dalton Transactions

JF - Dalton Transactions

SN - 1477-9226

IS - 6

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