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Issue 2, 2010
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Syntheses and structures of zirconium(IV) complexes supported by 2,6-di-adamantylaryloxide ligands and formation of arene-bridged dizirconium complexes with an inverse sandwich structure

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Abstract

The reaction of 2,6-di-adamantyl-4-R-phenol (ArROH, R = Me, tBu) with nBuLi in THF gave good yields of the lithiated derivatives (ArRO)Li(THF)2. Addition of 2 equiv. of (ArRO)Li(THF)2 to ZrCl4(THF)2 in THF afforded the base-free dichloride complexes (ArRO)ZrCl2 (R = Me 1a, tBu 1b). The dibenzyl derivative (ArMeO)2Zr(CH2Ph)22 was synthesized by addition of 2 equiv. of PhCH2MgCl to 1a in toluene. Reduction of the dichloride complexes 1a and 1b with KC8 in toluene led to the formation of the toluene-bridged dizirconium complexes [(ArRO)2Zr]2(μ-η66-C7H8) (R = Me 3a, tBu 3b). A similar reaction was carried out in benzene to produce the corresponding benzene-bridged analogue [(ArRO)2Zr]2(μ-η66-C6H6) (R = Me 4a, tBu 4b). Treatment of 3a with 2 equiv. of 1-azidoadamantane (AdN3) in THF resulted in the release of toluene and N2, generating the monomeric imide complex (ArMeO)2Zr(NAd)(thf) 5. When the analogous reaction was carried out in toluene, (ArMeO)2Zr(AdNN[double bond, length as m-dash]NNAd) 6 was obtained. Structures of (ArRO)Li(THF)2, 1a, 2 and 5 were determined by X-ray crystallography.

Graphical abstract: Syntheses and structures of zirconium(iv) complexes supported by 2,6-di-adamantylaryloxide ligands and formation of arene-bridged dizirconium complexes with an inverse sandwich structure

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Publication details

The article was received on 05 Jun 2009, accepted on 14 Aug 2009 and first published on 02 Sep 2009


Article type: Paper
DOI: 10.1039/B911082H
Dalton Trans., 2010,39, 484-491

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    Syntheses and structures of zirconium(IV) complexes supported by 2,6-di-adamantylaryloxide ligands and formation of arene-bridged dizirconium complexes with an inverse sandwich structure

    T. Watanabe, Y. Ishida, T. Matsuo and H. Kawaguchi, Dalton Trans., 2010, 39, 484
    DOI: 10.1039/B911082H

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