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Issue 4, 2013
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Synthesis, molecular structure, and stability of a zirconocene derivative with α-Keggin mono-aluminum-substituted polyoxotungstate

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Abstract

The synthesis and crystal structure of a zirconocene derivative with α-Keggin mono-aluminum-substituted polyoxotungstate, [α-PW11Al(OH)O39ZrCp2]26− (Cp = C5H5) (1), which was obtained by the reaction of α-Keggin mono-aluminum-substituted polyoxotungstate with a biscyclopentadienylzirconium(IV) complex, is described herein. Analytically pure, homogeneous, yellow crystals of the tetra-n-butylammonium salt of polyoxoanion 1, [(n-C4H9)4N]6[α-PW11Al(OH)O39ZrCp2]2 (TBA-1), were obtained from the ca. 1 : 1 reaction of [(n-C4H9)4N]4[α-PW11{Al(OH2)}O39] with Cp2Zr(OTf)2·THF (OTf = O3SCF3) in acetonitrile solution under an argon atmosphere, followed by precipitation from water and crystallization from acetonitrile. TBA-1 was characterized based on X-ray structure analysis, elemental analysis, thermogravimetric/differential thermal analysis (TG/DTA), Fourier transform infrared (FTIR), and solution (31P, 27Al, 19F, 1H, and 13C) nuclear magnetic resonance (NMR) spectroscopy. Single-crystal X-ray structure analysis revealed that the two {PW11AlO40} units are bridged by two “bent sandwich” Cp2Zr2+ fragments with C2 symmetry. Each zirconium center was bound to a terminal oxygen atom of the aluminum and tungsten sites and an edge-sharing oxygen atom at the Al–O–W linkage. Further, the stability towards water was investigated by NMR (31P, 1H, and 13C) and FTIR spectroscopy. The η5-cyclopentadienylzirconium fragments were not eliminated from the surface of [α-PW11{Al(OH2)}O39]4− even after 24 h exposure to 50 equiv. of water.

Graphical abstract: Synthesis, molecular structure, and stability of a zirconocene derivative with α-Keggin mono-aluminum-substituted polyoxotungstate

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Publication details

The article was received on 12 Sep 2012, accepted on 24 Oct 2012 and first published on 24 Oct 2012


Article type: Paper
DOI: 10.1039/C2DT32107F
Citation: Dalton Trans., 2013,42, 1129-1135
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    Synthesis, molecular structure, and stability of a zirconocene derivative with α-Keggin mono-aluminum-substituted polyoxotungstate

    C. N. Kato, Y. Makino, W. Unno and H. Uno, Dalton Trans., 2013, 42, 1129
    DOI: 10.1039/C2DT32107F

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