Rare-earth metal allyl and hydrido complexes supported by an (NNNN)-type macrocyclic ligand: synthesis, structure, and reactivity toward biomass-derived furanics |
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Authors: | Abinet Elise Martin Daniel Standfuss Sabine Kulinna Heiko Spaniol Thomas P Okuda Jun |
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Institution: | Institut für Anorganische Chemie, RWTH Aachen University, Landoltweg 1, 52056 Aachen, Germany. |
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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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Keywords: | allyl ligands hydrodeoxygenation hydrosilylation lanthanides macrocyclic ligands |
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