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

Said, M, Thornton-Pett, M and Bochmann, M (2001) Titanium and zirconium complexes with sterically hindered aryl-substituted iminophosphoranato ligands. Journal of the Chemical Society, Dalton Transactions (19). pp. 2844-2849.

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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.

Item Type: Article
Faculty \ School: Faculty of Science > School of Chemistry
Related URLs:
Depositing User: Rachel Smith
Date Deposited: 02 Nov 2010 17:48
Last Modified: 24 Jul 2019 17:42
URI: https://ueaeprints.uea.ac.uk/id/eprint/10477
DOI: 10.1039/b105038a

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