Rare-Earth Metal Allyl and Hydrido Complexes Supported by an (NNNN)-Type Macrocyclic Ligand: Synthesis, Structure, and Reactivity toward Biomass-Derived Furanics

Authors

  • Dipl.-Chem. Elise Abinet,

    1. Institut für Anorganische Chemie, RWTH Aachen University, Landoltweg 1, 52056 Aachen (Germany), Fax: (+49) 241-80-92644
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  • Dipl.-Chem. Daniel Martin,

    1. Institut für Anorganische Chemie, RWTH Aachen University, Landoltweg 1, 52056 Aachen (Germany), Fax: (+49) 241-80-92644
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  • Dipl.-Chem. Sabine Standfuss,

    1. Institut für Anorganische Chemie, RWTH Aachen University, Landoltweg 1, 52056 Aachen (Germany), Fax: (+49) 241-80-92644
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  • Dipl.-Chem. Heiko Kulinna,

    1. Institut für Anorganische Chemie, RWTH Aachen University, Landoltweg 1, 52056 Aachen (Germany), Fax: (+49) 241-80-92644
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  • Dr. Thomas P. Spaniol,

    1. Institut für Anorganische Chemie, RWTH Aachen University, Landoltweg 1, 52056 Aachen (Germany), Fax: (+49) 241-80-92644
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  • Prof. Dr. Jun Okuda

    Corresponding author
    1. Institut für Anorganische Chemie, RWTH Aachen University, Landoltweg 1, 52056 Aachen (Germany), Fax: (+49) 241-80-92644
    • Institut für Anorganische Chemie, RWTH Aachen University, Landoltweg 1, 52056 Aachen (Germany), Fax: (+49) 241-80-92644
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Abstract

The preparation and characterization of a series of neutral rare-earth metal complexes [Ln(Me3TACD)(η3-C3H5)2] (Ln=Y, La, Ce, Pr, Nd, Sm) supported by the 1,4,7-trimethyl-1,4,7,10-tetraazacyclododecane anion (Me3TACD) are reported. Upon treatment of the neutral allyl complexes [Ln(Me3TACD)(η3-C3H5)2] with Brønsted acids, monocationic allyl complexes [Ln(Me3TACD)(η3-C3H5)(thf)2][B(C6X5)4] (Ln=La, Ce, Nd, X=H, F) were isolated and characterized. Hydrogenolysis gave the hydride complexes [Ln(Me3TACD)H2]n (Ln=Y, n=3; La, n=4; Sm). X-ray crystallography showed the lanthanum hydride to be tetranuclear. Reactivity studies of [Ln(Me3TACD)R2]n (R=η3-C3H5, n=0; R=H, n=3,4) towards furan derivatives includes hydrosilylation and deoxygenation under ring-opening conditions.

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