title: Rare-earth metal allyl and hydrido complexes supported by an (NNNN)-type macrocyclic ligand: synthesis, structure, and reactivity toward biomass-derived furanics.
abstract: The preparation and characterization of a series of neutral rare-earth metal complexes [Ln(Me(3)TACD)(η(3)-C(3)H(5))(2)] (Ln=Y, La, Ce, Pr, Nd, Sm) supported by the 1,4,7-trimethyl-1,4,7,10-tetraazacyclododecane anion (Me(3)TACD(-)) are reported. Upon treatment of the neutral allyl complexes [Ln(Me(3)TACD)(η(3)-C(3)H(5))(2)] with Brønsted acids, monocationic allyl complexes [Ln(Me(3)TACD)(η(3)-C(3)H(5))(thf)(2)][B(C(6)X(5))(4)] (Ln=La, Ce, Nd, X=H, F) were isolated and characterized. Hydrogenolysis gave the hydride complexes [Ln(Me(3)TACD)H(2)](n) (Ln=Y, n=3; La, n=4; Sm). X-ray crystallography showed the lanthanum hydride to be tetranuclear. Reactivity studies of [Ln(Me(3)TACD)R(2)](n) (R=η(3)-C(3)H(5), n=0; R=H, n=3,4) towards furan derivatives includes hydrosilylation and deoxygenation under ring-opening conditions.
authors.affiliation: Institut für Anorganische Chemie, RWTH Aachen University, Landoltweg 1, 52056 Aachen, Germany.
authors.forename: Elise
authors.initials: E
authors.lastname: Abinet
authors.forename: Daniel
authors.initials: D
authors.lastname: Martin
authors.forename: Sabine
authors.initials: S
authors.lastname: Standfuss
authors.forename: Heiko
authors.initials: H
authors.lastname: Kulinna
authors.forename: Thomas P
authors.initials: TP
authors.lastname: Spaniol
authors.forename: Jun
authors.initials: J
authors.lastname: Okuda
mesh_terms: D018533:Biomass; D002384:Catalysis; D018360:Crystallography, X-Ray; D005663:Furans / Q000138:chemical synthesis* / Q000737:chemistry*; D028581:Lanthanoid Series Elements / Q000737:chemistry*; D007811:Lanthanum / Q000737:chemistry*; D008024:Ligands; D047028:Macrocyclic Compounds / Q000737:chemistry*; D008674:Metals, Rare Earth / Q000737:chemistry*; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D005663:Furans; D028581:Lanthanoid Series Elements; D008024:Ligands; D047028:Macrocyclic Compounds; D008674:Metals, Rare Earth; D009942:Organometallic Compounds; D007811:Lanthanum