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Small Changes Have Consequences: Lessons from Tetrabenzyltitanium and -zirconium Surface Organometallic Chemistry

Authors

  • Dr. Nicolas Popoff,

    1. C2P2 (CNRS-UMR 5265), Université Lyon 1, ESCPE Lyon, 43 Boulevard du 11 Novembre 1918, 69626 Villeurbanne Cedex (France)
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  • Dr. Jeff Espinas,

    1. C2P2 (CNRS-UMR 5265), Université Lyon 1, ESCPE Lyon, 43 Boulevard du 11 Novembre 1918, 69626 Villeurbanne Cedex (France)
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  • Dr. Jérémie Pelletier,

    1. C2P2 (CNRS-UMR 5265), Université Lyon 1, ESCPE Lyon, 43 Boulevard du 11 Novembre 1918, 69626 Villeurbanne Cedex (France)
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  • Benoît Macqueron,

    1. C2P2 (CNRS-UMR 5265), Université Lyon 1, ESCPE Lyon, 43 Boulevard du 11 Novembre 1918, 69626 Villeurbanne Cedex (France)
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  • Dr. Kai C. Szeto,

    1. C2P2 (CNRS-UMR 5265), Université Lyon 1, ESCPE Lyon, 43 Boulevard du 11 Novembre 1918, 69626 Villeurbanne Cedex (France)
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  • Olivier Boyron,

    1. C2P2 (CNRS-UMR 5265), Université Lyon 1, ESCPE Lyon, 43 Boulevard du 11 Novembre 1918, 69626 Villeurbanne Cedex (France)
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  • Dr. Christophe Boisson,

    1. C2P2 (CNRS-UMR 5265), Université Lyon 1, ESCPE Lyon, 43 Boulevard du 11 Novembre 1918, 69626 Villeurbanne Cedex (France)
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  • Dr. Iker Del Rosal,

    1. LPCNO (CNRS-UMR 5215), Université de Toulouse, INSA, UPS, 135 Avenue de Rangueil, 31077 Toulouse (France)
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  • Dr. Laurent Maron,

    Corresponding author
    1. LPCNO (CNRS-UMR 5215), Université de Toulouse, INSA, UPS, 135 Avenue de Rangueil, 31077 Toulouse (France)
    • LPCNO (CNRS-UMR 5215), Université de Toulouse, INSA, UPS, 135 Avenue de Rangueil, 31077 Toulouse (France)
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  • Dr. Aimery De Mallmann,

    1. C2P2 (CNRS-UMR 5265), Université Lyon 1, ESCPE Lyon, 43 Boulevard du 11 Novembre 1918, 69626 Villeurbanne Cedex (France)
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  • Dr. Régis M. Gauvin,

    Corresponding author
    1. UCCS (CNRS-UMR 8181), Université Lille Nord de France, USTL-ENSCL, 59652 Villeneuve d'Ascq (France)
    • UCCS (CNRS-UMR 8181), Université Lille Nord de France, USTL-ENSCL, 59652 Villeneuve d'Ascq (France)
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  • Dr. Mostafa Taoufik

    Corresponding author
    1. C2P2 (CNRS-UMR 5265), Université Lyon 1, ESCPE Lyon, 43 Boulevard du 11 Novembre 1918, 69626 Villeurbanne Cedex (France)
    • C2P2 (CNRS-UMR 5265), Université Lyon 1, ESCPE Lyon, 43 Boulevard du 11 Novembre 1918, 69626 Villeurbanne Cedex (France)
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Abstract

Homoleptic benzyl derivatives of titanium and zirconium have been grafted onto silica that was dehydroxylated at 200 and 700 °C, thereby affording bi-grafted and mono-grafted single-site species, respectively, as shown by a combination of experimental techniques (IR, MAS NMR, EXAFS, and elemental analysis) and theoretical calculations. Marked differences between these compounds and their neopentyl analogues are discussed and rationalized by using DFT. These differences were assigned to the selectivity of the grafting process, which, depending on the structure of the molecular precursors, led to different outcomes in terms of the mono- versus bi-grafted species for the same surface concentration of silanol species. The benzylzirconium derivatives were active towards ethylene polymerization in the absence of an activator and the bi-grafted species displayed higher activity than their mono-grafted analogues. In contrast, the benzyltitanium and neopentylzirconium counterparts were not active under similar reaction conditions.

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